CN105914298B - Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer - Google Patents

Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer Download PDF

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CN105914298B
CN105914298B CN201610321684.4A CN201610321684A CN105914298B CN 105914298 B CN105914298 B CN 105914298B CN 201610321684 A CN201610321684 A CN 201610321684A CN 105914298 B CN105914298 B CN 105914298B
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王悦
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Jilin University
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    • 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
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

One kind take bioxindol derivative (its in alcohol/water solvable) as the polymer photovoltaic cell of embellishing cathode interface layer, belongs to polymer photovoltaic cell technical field.Bioxindol derivative interface-modifying layer is between the active layer and cathode of photovoltaic cell, can effectively improve the energy conversion efficiency of device.Device architecture successively include: the ITO that is attached on transparent glass as anode, PEDOT:PSS as anode modification layer, PTB7:PC71BM is as active layer, and comprising the bioxindol derivant material of the present invention that contains as embellishing cathode interface layer, metal Al is as cathode.With PTB7:PC71BM is the photovoltaic device of active layer, and the compounds of this invention IIDTh-C of 8 nano thickness is added6After NSB is as embellishing cathode interface layer, device performance is obviously improved, and current density is from 13.98mA cm‑2It is promoted to 16.90mA cm‑2, voltage is promoted to 0.75V from 0.65V, and fill factor is promoted to 71.6% from 54.0%, and photoelectric conversion efficiency is promoted to 9.08% from 5.12%.

Description

Using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer
Technical field
The invention belongs to polymer photovoltaic cell technical fields, and in particular to a kind of with bioxindol derivative, (it is in alcohol/water In it is solvable) be embellishing cathode interface layer polymer photovoltaic cell.
Background technique
Polymer photovoltaic cell is due to that can apply spraying printing technology to produce low in cost and flexible substrates devices Part is so have been a great concern.Currently, the energy conversion efficiency (PCE) of polymer photovoltaic cell has broken through 10.0%, It has made significant headway in terms of design of material, device optimization and interfacial process, but the cathode between active layer and electrode Interface-modifying layer is even more important in terms of exciton transfer and separation, and which determine the performance and stability of device.
Embellishing cathode interface layer is improved, reduces charge-trapping/separation obstacle formation Ohmic contact promotion PCE and draws in recent years Play more and more concerns.Common embellishing cathode interface material includes inorganic salts (such as LiF, CsCO3Deng), metal oxide (ZnO, TiO2Deng) and with alcohol/water-soluble matter small organic molecule and polymer, compared to other embellishing cathode interfaces Material, the small organic molecule of alcohol/water dissolution and the advantage of polymer are to be deposited and right in device fabrication processes with antivacuum Environmental-friendly method, there are also have general applicability to different active layer and metal electrode.Because it is organic to be dissolved in alcohol/water Small molecule or polymer can avoid damage to active layer.Alcohol/water dissolution small organic molecule and polymer are as cathode interface Decorative material has prospect in the development of polymer photovoltaic cell very much.Compared to polymer cathode modifying interface material, You Ji little Molecule has the advantages that product is easy to purify and molecular structure determines, develops in recent years very fast, 2014 miscellaneous in Science Todd.Emrick et al. has synthesized alcohol/water-soluble small molecule embellishing cathode interface material based on fullerene in will, with PTB7:PC71BM is active layer, and PCE is more than 8.5%, and the problem of be investigated interfacial layer thickness and metal electrode universality (Science,2014,346,441–444).2015, Ge Zi justice seminar delivered conjunction on Nature Photonics magazine At non-conjugated Sulfonates small molecule as embellishing cathode interface material, with PTB7:PC71BM is active layer, realizes PCE and reaches To 10.02% this high energy conversion efficiency (Nat.Photonics, 2015,9,502-524).
We are good due to having using the bioxindol derivative with pyridiniujm or sulfonate modification group in the present invention Water or the deliquescent pyridiniujm of alcohol or sulfonate modification group introduce, and make such material favorable solubility in alcohol/water.In addition exist The two sides of bioxindol group may be incorporated into thiophene, two company's thiophene, three company's thiophene and benzene radicals and carry out substituent group, be come with this Improve the characteristic that be combined with each other of material and organic photovoltaic devices active layer.Therefore these materials can be used as embellishing cathode interface layer Applied in polymer photovoltaic cell.It simultaneously can be effectively by comparing a series of this performance of bioxindol molecules on device Give us the following compound direction for solar battery embellishing cathode interface material.
Summary of the invention
The application of the purpose of the present invention is to provide one kind in alcohol/water soluble bioxindol derivative, that is, provide a kind of Using bioxindol derivative as the application in the high-performance polymer photovoltaic cell of embellishing cathode interface layer.
Bioxindol derivative embellishing cathode interface material according to the present invention, general structure are as follows:
Wherein, n is 4 to 10 integer, and R1 can be two kinds of groups of amido pyridiniujm or dimethylamine sulfonate inner salt, and R2 can be with It is the groups such as H, thiophene, two company's thiophene, three company's thiophene, phenyl ring.
It specifically describes, compound representative configurations formula according to the present invention includes compound as follows:
The integer of n=4~10.
Compound synthesis route according to the present invention is as follows:
Compound of the present invention can be used for preparing polymer photovoltaic cell, particularly be used to prepare polymer light The embellishing cathode interface layer of battery is lied prostrate, which is between the active layer and cathode of photovoltaic cell.As shown in Figure 1, Specific device architecture is sequentially are as follows: the ITO being attached on transparent glass is anode, PEDOT-PSS (poly- 3,4- enedioxy thiophene Pheno-poly styrene sulfonate is bought in German Baytron company, model: PVP Al 4083) be anode modification layer, PTB7: PC71BM (mass ratio is 1.8~2.2:2.7~3.3) is active layer, and compound of the present invention is embellishing cathode interface layer, Metal Al is cathode.The following figure is PTB7, PC71The molecular structural formula of BM, PEDOT and PSS.
With PTB7:PC71BM is the photovoltaic device of active layer, and the compounds of this invention IIDTh-C of 8 nano thickness is added6NSB After embellishing cathode interface layer, device performance is obviously improved, and current density is from 13.98mA cm-2It is promoted to 16.90mA cm-2, voltage is promoted to 0.75V from 0.65V, and fill factor is promoted to 71.6% from 54.0%, and photoelectric conversion efficiency is from 5.12% It is promoted to 9.08%, as shown in Figure 2.
Detailed description of the invention
Fig. 1: the photovoltaic device structural schematic diagram of application material of the present invention preparation；
Fig. 2: the photovoltaic device I-V performance map of application compound of the present invention preparation.
As shown in Figure 1, the names of the parts are as follows: clear glass substrate 1, the anode ITO oxide of attachment on the glass surface (PTB7: poly- [bis- ((2- ethyl is by 4,8- by conductive layer 2, PEDOT-PSS anode modification layer 3, device active layers PTB7:PC71BM Base) oxygroup] the bis- Dithiophenes of benzo [1,2-b:4,5-b'] 2,6-] [the fluoro- 2- of 3- [(2- ethylhexyl) carbonyl] thieno [3,4- B] thiophene ester], buy in Canadian 1-Material company；PC71BM:[6,6]-phenyl-C71- methyl butyrate, it buys in beauty ADS of state) 4, the embellishing cathode interface layer 5 comprising compound of the present invention, metal Al cathode 6.
As shown in Fig. 2, its characteristic of the photovoltaic device based on the compounds of this invention IIDTh-NSB is as follows: open-circuit voltage is 0.75V, short-circuit current density 16.90mAcm-2, fill factor 71.6%, being computed incident photon-to-electron conversion efficiency is 9.08%.
Wherein for synthesizing the raw material of isoindigo cyan molecule: 2- indolone, indoles 2,3- diketone is all purchase in lark prestige J&K Company, for synthesizing the raw material of 6- bromine isoindigo cyan molecule: (purchase is in lark prestige J&K company, CAS:6326-79- for 6- bromo-isatin 0), 6- bromo indole -2- ketone is also all bought in lark prestige J&K company.And the alkyl chain for being used for synthetic intermediate includes: 1,4- dibromo Butane, 1, pentamethylene bromide, 1,6- dibromo-hexane, 1,7- dibromo-heptane, 1,8- bis- bromooctane, 1,9- dibromo nonane, 1,10- bis- Bromo-decane and dimethylamine hydrochloride, 1,3- propane sultone, phenyl boric acid, 2- thienyl boric acid, bigeminy thienyl boric acid, three connect thiophene Boric acid is all purchase in An Naiji Energy company.
Specific embodiment
Embodiment 1: compound IID-C4The synthesis of PyBr:
By the compound bioxindol synthesized according to document (Eur.J.Med.Chem, 2014,86,165-174) (2.0g, 7.7mmol), Isosorbide-5-Nitrae-dibromobutane (8.2g, 38.4mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.4mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder solid IID-C4After Br, by compound IID-C4Br (540.0mg, 1.0mmol), pyridine 20mL are placed in It is heated to reflux 8 hours in 50mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature, filters, filter cake is with 100mL CH2Cl2Washing, Drying, obtains (600.0mg, yield 87.0%).The molecular ion quality that mass spectral analysis determines are as follows: 690.6 (calculated value are as follows: 690.1)；Theoretical elemental content (%) C34H36Br2N4O2: C, 58.97；H, 5.24；N, 8.09；Constituent content (%): C is surveyed, 59.37；H, 5.66；N, 8.18.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 2: compound IID-C5The synthesis of PyBr:
IID-C5The synthesis of PyBr and IID-C4PyBr method is completely the same, only using 1,5 dibromo pentanes as raw material (red solid, yield 86.0%).The molecular ion quality that mass spectral analysis determines are as follows: 718.7 (calculated values are as follows: 718.1)；It is theoretical Constituent content (%) C36H40Br2N4O2: C, 60.01；H, 5.60；N, 7.78；Survey constituent content (%): C, 59.95；H, 5.65；N, 7.91.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 3: compound IID-C6The synthesis of PyBr:
IID-C6The synthesis of PyBr and IID-C4PyBr method is completely the same, only using 1,6- dibromo-hexane as raw material (red solid, yield 87.5%).The molecular ion quality that mass spectral analysis determines are as follows: 746.5 (calculated values are as follows: 746.1)；It is theoretical Constituent content (%) C38H44Br2N4O2: C, 60.97；H, 5.92；N, 7.48；Survey constituent content (%): C, 60.85；H, 5.85；N, 7.71.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 4: compound IID-C7The synthesis of PyBr:
IID-C7The synthesis of PyBr and IID-C4PyBr method is completely the same, only (red as raw material heptan using 1,7- dibromo Color solid, yield 85.3%).The molecular ion quality that mass spectral analysis determines are as follows: 774.6 (calculated values are as follows: 774.2)；Theoretical member Cellulose content (%) C40H48Br2N4O2: C, 61.86；H, 6.23；N, 7.21；Survey constituent content (%): C, 61.95；H, 6.41； N, 7.04.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 5: compound IID-C8The synthesis of PyBr:
IID-C8The synthesis of PyBr and IID-C4PyBr method is completely the same, only using 1,8-, bis- bromooctane as raw material (red solid, yield 89.3%).The molecular ion quality that mass spectral analysis determines are as follows: 802.5 (calculated values are as follows: 802.2)；It is theoretical Constituent content (%) C42H52Br2N4O2: C, 62.69；H, 6.51；N, 6.96；Survey constituent content (%): C, 62.51；H, 6.33；N, 6.84.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 6: compound IID-C9The synthesis of Br:
IID-C9The synthesis of Br and IID-C4Br method is completely the same, only (red as raw material using 1,9- dibromo nonane Solid, yield 40.0%).The molecular ion quality that mass spectral analysis determines are as follows: 672.8 (calculated values are as follows: 672.2)；Theoretical elemental Content (%) C34H46Br2N2O2: C, 60.54；H,6.87；N, 4.15；Survey constituent content (%): C, 60.35；H, 6.96；N, 4.04.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 7: compound IID-C10The synthesis of PyBr:
IID-C10The synthesis of PyBr and IID-C4PyBr method is completely the same, only using 1,10- dibromo-decane as former Expect (red solid, yield 85.5%).The molecular ion quality that mass spectral analysis determines are as follows: 860.0 (calculated values are as follows: 858.3)；Reason Argument cellulose content (%) C46H60Br2N4O2: C, 64.18；H, 7.03；N, 6.51；Survey constituent content (%): C, 64.28；H, 6.97；N, 6.20.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 8: compound IID-C4The synthesis of NSB:
By the compound bioxindol synthesized according to document (Eur.J.Med.Chem, 2014,86,165-174) (2.0g, 7.7mmol), Isosorbide-5-Nitrae-dibromobutane (8.2g, 38.4mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.4mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder solid IID-C4After Br, by compound IID-C4Br (540.0mg, 1.0mmol), dimethylamine hydrochloride (850.0mg, 5.1mmol), Anhydrous potassium carbonate (710.0mg, 5.1mmol), n,N-Dimethylformamide (DMF) 25mL are placed in It is heated to 100 DEG C of 20 hours of reaction in 100mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature revolving and removes solvent, extract drying Then filtering revolving separates (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) with the method that column chromatographs, obtains To red powder solid IID-C4N, then by compound IID-C4N (200.0mg, 0.4mmol), 1,3- propane sultone (488.0mg, 4.0mmol), anhydrous tetrahydro furan 15mL are placed in 50mL bottle with two necks, and it is small that 12 are heated to reflux in nitrogen atmosphere When, it is cooled to room temperature and boils off solvent, filter, filter cake is with 100mL CH2Cl2Washing, drying, obtains red powder product (235.0mg, yield 83.3%).The molecular ion quality that mass spectral analysis determines are as follows: 707.1 (calculated values are as follows: 706.3)；It is theoretical Constituent content (%) C34H50N4O8S2: C, 57.77；H,7.13；N, 7.93；S, 9.07；Survey constituent content (%): C, 57.44； H, 6.90；N, 7.88；S, 9.25.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 9: compound IID-C5The synthesis of NSB:
IID-C5The synthesis of NSB and IID-C4NSB method is completely the same, only uses 1, pentamethylene bromide is (red as raw material Color solid, yield 87.0%).The molecular ion quality that mass spectral analysis determines are as follows: 734.8 (calculated values are as follows: 734.3.5)；It is theoretical Constituent content (%) C36H54N4O8S2: C, 58.83；H,7.41；N, 7.62；S, 8.72；Survey constituent content (%): C, 58.98； H, 7.54；N, 7.34；S, 8.63.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 10: compound IID-C6The synthesis of NSB:
IID-C6The synthesis of NSB and IID-C4NSB method is completely the same, only (red as raw material using 1,6- dibromo-hexane Color solid, yield 86.4%).The molecular ion quality that mass spectral analysis determines are as follows: 763.2 (calculated values are as follows: 762.4)；Theoretical member Cellulose content (%) C38H58N4O8S2: C, 59.82；H,7.66；N, 7.34；S, 8.40；Survey constituent content (%): C, 59.62；H, 7.65；N, 7.41；S, 8.58.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 11: compound IID-C7The synthesis of NSB:
IID-C7The synthesis of NSB and IID-C4NSB method is completely the same, only (red as raw material using 1,7- dibromo-heptane Color solid, yield 82.0%).The molecular ion quality that mass spectral analysis determines are as follows: 791.0 (calculated values are as follows: 790.4)；Theoretical member Cellulose content (%) C40H62N4O8S2: C, 60.73；H,7.90；N, 7.08；S, 8.11；Survey constituent content (%): C, 60.95；H, 7.87；N, 7.04；S, 7.96.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 12: compound IID-C8The synthesis of NSB:
IID-C8The synthesis of NSB and IID-C4NSB method is completely the same, only (red as raw material using 1,8-, bis- bromooctane Color solid, yield 90.0%).The molecular ion quality that mass spectral analysis determines are as follows: 819.1 (calculated values are as follows: 818.4)；Theoretical member Cellulose content (%) C42H66N4O8S2: C, 61.59；H,8.12；N, 6.84；S, 7.83；Survey constituent content (%): C, 61.37；H, 8.07；N, 6.534；S, 7.91.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 13: compound IID-C9The synthesis of NSB:
IID-C9The synthesis of NSB and IID-C4NSB method is completely the same, only (red as raw material using 1,9- dibromo nonane Color solid, yield 87.5%).The molecular ion quality that mass spectral analysis determines are as follows: 847.1 (calculated values are as follows: 846.5)；Theoretical member Cellulose content (%) C44H70N4O8S2: C, 62.38；H,8.33；N, 6.61；S, 7.57；Survey constituent content (%): C, 62.56；H, 8.17；N, 6.33；S, 7.28.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 14: compound IID-C10The synthesis of NSB:
IID-C10The synthesis of NSB and IID-C4NSB method is completely the same, only using 1,10- dibromo-decane as raw material (red solid, yield 82.5%).The molecular ion quality that mass spectral analysis determines are as follows: 875.1 (calculated values are as follows: 874.5)；It is theoretical Constituent content (%) C46H74N4O8S2: C, 63.13；H,8.52；N, 6.40；S, 7.33；Survey constituent content (%): C, 63.01； H, 8.73；N, 6.45；S, 7.10.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 15: compound IIDTh-C4The synthesis of PyBr:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4 (6), 1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere It is heated to 105 DEG C after first stirring at normal temperature 4 hours to react 14 hours, is cooled to room temperature for solution and red is obtained by revolving method Solid, extraction dry filter revolving, then separates (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) with column chromatography method Obtain red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- tributyl first tin Alkylthrophene (1.09g, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyls) Phosphine (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, injects the distilled nothing of 30ml with syringe under nitrogen atmosphere Water tetrahydrofuran, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, remove It goes after Dewar heating reflux reaction 12 hours, after being cooled to room temperature, solution obtains black solid by revolving method, extracts drying Then filtering revolving is obtained red with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Black powder product IIDTh-C4Br, finally by compound IIDTh-C4Br (175.0mg, 0.25mmol), pyridine 20mL are placed It is heated to reflux 8 hours in 50mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature, filters, filter cake is with 100mL CH2Cl2It washes It washs, dries, obtain (170.0mg, yield 79.9%).The molecular ion quality that mass spectral analysis determines are as follows: 854.6 (calculated value are as follows: 854.1)；Theoretical elemental content (%) C42H40Br2N4O2S2: C, 58.88；H, 4.71；N, 6.54；S, 7.48；Survey constituent content (%): C, 58.99；H, 4.73；N, 6.69；S, 7.77.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 16: compound IIDTh-C5The synthesis of PyBr:
IIDTh-C5The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, only uses 1, pentamethylene bromide conduct Raw material (reddish black solid, yield 85.0%).The molecular ion quality that mass spectral analysis determines are as follows: 882.8 (calculated value are as follows: 882.1)；Theoretical elemental content (%) C44H44Br2N2O2S2: C, 59.73；H, 5.01；N, 6.33；S, 7.25；Survey constituent content (%): C, 59.97；H, 4.95；N, 6.29；S, 7.38.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 17: compound IIDTh-C6The synthesis of PyBr:
IIDTh-C6The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, only uses the conduct of 1,6- dibromo-hexane Raw material (reddish black solid, yield 78.7%).The molecular ion quality that mass spectral analysis determines are as follows: 910.8 (calculated value are as follows: 910.2)；Theoretical elemental content (%) C46H48Br2N2O2S2: C, 60.53；H, 5.30；N, 6.14；S, 7.02；Survey constituent content (%): C, 60.77；H, 5.36；N, 6.03；S, 6.99.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 18: compound IIDTh-C7The synthesis of PyBr:
IIDTh-C7The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, only uses the conduct of 1,7- dibromo-heptane Raw material (reddish black solid, yield 80.9%).The molecular ion quality that mass spectral analysis determines are as follows: 938.4 (calculated value are as follows: 938.2)；Theoretical elemental content (%) C48H52Br2N2O2S2: C, 61.27；H, 5.57；N, 5.95；S, 6.81 actual measurement constituent contents (%): C, 61.53；H, 5.68；N, 5.77；S, 6.80.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 19: compound IIDTh-C8The synthesis of PyBr:
IIDTh-C8The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, only uses 1,8-, bis- bromooctane conduct Raw material (reddish black solid, yield 86.0%).The molecular ion quality that mass spectral analysis determines are as follows: 966.7 (calculated value are as follows: 966.2)；Theoretical elemental content (%) C50H56Br2N2O2S2: C, 61.98；H, 5.83；N, 5.78；S, 6.62 actual measurement constituent contents (%): C, 61.90；H, 5.92；N, 5.88；S, 6.51.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 20: compound IIDTh-C9The synthesis of PyBr:
IIDTh-C9The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, only uses the conduct of 1,9- dibromo nonane Raw material (reddish black solid, yield 81.5%).The molecular ion quality that mass spectral analysis determines are as follows: 994.6 (calculated value are as follows: 994.3)；Theoretical elemental content (%) C52H60Br2N2O2S2: C, 62.64；H, 6.07；N, 5.62；S, 6.43 actual measurement constituent contents (%): C, 62.78；H, 6.22；N, 5.43；S, 6.40.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 21: compound IIDTh-C10The synthesis of PyBr:
IIDTh-C10The synthesis of PyBr and IIDTh-C4PyBr method is completely the same, is only made using 1,10- dibromo-decane For raw material (reddish black solid, yield 79.2%).The molecular ion quality that mass spectral analysis determines are as follows: 1022.6 (calculated value are as follows: 1022.3)；Theoretical elemental content (%) C54H64Br2N2O2S2: C, 63.27；H, 6.29；N, 5.47；S, 6.26 actual measurement constituent contents (%): C, 63.55；H, 6.17；N, 5.50；S, 6.10.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 22: compound IIDTh-C4The synthesis of NSB:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- tributylstannyl Base thiophene (1.09g, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, distilled anhydrous with syringe injection 30ml under nitrogen atmosphere Tetrahydrofuran, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, remove Heating reflux reaction 12 hours after Dewar, after being cooled to room temperature, solution obtains black solid by revolving method, extracts dried Then filter revolving is obtained red-black with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Color powdery product IIDTh-C4Br, then by compound IIDTh-C4Br (700.0mg, 1.0mmol), dimethylamine hydrochloride (850.0mg, 5.1mmol), Anhydrous potassium carbonate (710.0mg, 5.1mmol), n,N-Dimethylformamide (DMF) 25mL are placed in It is heated to 100 DEG C of 20 hours of reaction in 100mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature revolving and removes solvent, extract drying Then filtering revolving separates (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) with the method that column chromatographs, obtains To reddish black pulverulent solids IIDTh-C4N, finally by compound IIDTh-C4N (310.0mg, 0.5mmol), 1,3- propane sulphur Acid lactone (488.0mg, 4.0mmol), anhydrous tetrahydro furan 15mL are placed in 50mL bottle with two necks, are heated to reflux in nitrogen atmosphere It 12 hours, is cooled to room temperature and boils off solvent, filter, filter cake is with 100mL CH2Cl2Washing, drying, obtains black powder product IIDTh-C4NSB (black solid, 335.0mg, yield 78.1%).The molecular ion quality that mass spectral analysis determines are as follows: 870.8 (calculated value are as follows: 870.3)；Theoretical elemental content (%) C42H54N4O8S2: C, 58.35；H, 6.38；N, 6.33；S, 14.49；It is real Survey constituent content (%): C, 58.15；H, 6.54；N, 6.34；S, 14.63.Above-mentioned analysis the result shows that, the product of acquisition is pre- The product of meter.
Embodiment 23: compound IIDTh-C5The synthesis of NSB:
IIDTh-C5The synthesis of NSB and IIDTh-C4NSB method is completely the same, only uses 1, pentamethylene bromide is as former Expect (black solid, yield 82.8%).The molecular ion quality that mass spectral analysis determines are as follows: 898.8 (calculated values are as follows: 898.3)；Reason Argument cellulose content (%) C44H58N4O8S2: C, 58.77；H, 6.50；N, 6.23；S, 14.26；Constituent content (%): C is surveyed, 58.42；H, 6.78；N, 6.10；S, 14.37.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 24: compound IIDTh-C6The synthesis of NSB:
IIDTh-C6The synthesis of NSB and IIDTh-C4NSB method is completely the same, only using 1,6- dibromo-hexane as former Expect (black solid, yield 75.3%).The molecular ion quality that mass spectral analysis determines are as follows: 927.0 (calculated values are as follows: 926.4)；Reason Argument cellulose content (%) C46H62N4O8S2: C, 59.58；H, 6.74；N, 6.04；S, 13.83；Constituent content (%): C is surveyed, 59.75；H, 6.70；N, 5.91；S, 13.44.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 25: compound IIDTh-C7The synthesis of NSB:
IIDTh-C7The synthesis of NSB and IIDTh-C4NSB method is completely the same, only using 1,7- dibromo-heptane as former Expect (black solid, yield 81.4%).The molecular ion quality that mass spectral analysis determines are as follows: 955.1 (calculated values are as follows: 954.4)；Reason Argument cellulose content (%) C48H66N4O8S2: C, 60.35；H, 6.96；N, 5.86；S, 13.42；Constituent content (%): C is surveyed, 60.55；H, 6.70；N, 5.91；S, 13.44.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 26: compound IIDTh-C8The synthesis of NSB:
IIDTh-C8The synthesis of NSB and IIDTh-C4NSB method is completely the same, only using 1,8-, bis- bromooctane as former Expect (black solid, yield 86.3%).The molecular ion quality that mass spectral analysis determines are as follows: 983.1 (calculated values are as follows: 982.4)；Reason Argument cellulose content (%) C50H70N4O8S2: C, 61.07；H, 7.18；N, 5.70；S, 13.04；Constituent content (%): C is surveyed, 61.25；H, 7.09；N, 5.31；S, 13.01 above-mentioned analyses the result shows that, the product of acquisition is estimated product.
Embodiment 27: compound IIDTh-C9The synthesis of NSB:
IIDTh-C9The synthesis of NSB and IIDTh-C4NSB method is completely the same, only using 1,9- dibromo nonane as former Expect (black solid, yield 80.3%).The molecular ion quality that mass spectral analysis determines are as follows: 1015.0 (calculated values are as follows: 1010.4)； Theoretical elemental content (%) C52H74N4O8S2: C, 61.75；H, 7.37；N, 5.54；S, 12.68；Constituent content (%): C is surveyed, 61.99；H, 7.21；N, 5.38；S, 13.00 above-mentioned analyses the result shows that, the product of acquisition is estimated product.
Embodiment 28: compound IIDTh-C10The synthesis of NSB:
IIDTh-C10The synthesis of NSB and IIDTh-C4NSB method is completely the same, only uses the conduct of 1,10- dibromo-decane Raw material (black solid, yield 85.5%).The molecular ion quality that mass spectral analysis determines are as follows: 1039.1 (calculated value are as follows: 1038.5)；Theoretical elemental content (%) C54H78N4O8S2: C, 62.40；H, 7.56；N, 5.39；S, 12.34；Survey constituent content (%): C, 62.31；H, 7.59；N, 5.42；S, 12.55 above-mentioned analyses the result shows that, the product of acquisition is estimated product.
Embodiment 29: compound IIDDTh-C4The synthesis of PyBr:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- bis- connect thienyl boric acid (590mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, distilled anhydrous with syringe injection 30ml under nitrogen atmosphere Tetrahydrofuran, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, remove Heating reflux reaction 12 hours after Dewar, after being cooled to room temperature, solution obtains black solid by revolving method, extracts dried Then filter revolving is obtained red-black with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Color powdery product IIDDTh-C4Br, finally by compound IIDDTh-C4Br (175.0mg, 0.25mmol), pyridine 20mL are placed It is heated to reflux 8 hours in 50mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature, filters, filter cake is with 100mL CH2Cl2It washes It washs, dries, obtain black solid, 230mg, yield 91.0%.The molecular ion quality that mass spectral analysis determines are as follows: 1018.8 (meters Calculation value are as follows: 1018.1)；Theoretical elemental content (%) C50H44Br2N4O2S4: C, 58.82；H, 4.34；N, 5.49；S, 12.56；It is real Survey constituent content (%): C, 58.88；H, 4.17；N, 5.53；S, 12.47.Above-mentioned analysis the result shows that, the product of acquisition is pre- The product of meter.
Embodiment 30: compound IIDDTh-C5The synthesis of PyBr:
IIDDTh-C5The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, only uses 1, pentamethylene bromide is made For raw material (black solid, yield 90.0%).The molecular ion quality that mass spectral analysis determines are as follows: 1046.8 (calculated value are as follows: 1046.1)；Theoretical elemental content (%) C52H48Br2N4O2S4: C, 59.54；H, 4.61；N, 5.34；S, 12.22；Actual measurement element contains Measure (%): C, 59.67；H, 4.57；N, 5.12；S, 12.05.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 31: compound IIDDTh-C6The synthesis of PyBr:
IIDDTh-C6The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, is only made using 1,6- dibromo-hexane For raw material (black solid, yield 88.6%).The molecular ion quality that mass spectral analysis determines are as follows: 1074.6 (calculated value are as follows: 1074.1)；Theoretical elemental content (%) C54H52Br2N4O2S4: C, 60.22；H, 4.87；N, 5.20；S, 11.91；Actual measurement element contains Measure (%): C, 60.35；H, 4.75；N, 5.34；S, 11.85.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 32: compound IIDDTh-C7The synthesis of PyBr:
IIDDTh-C7The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, is only made using 1,7- dibromo-heptane For raw material (black solid, yield 84.8%).The molecular ion quality that mass spectral analysis determines are as follows: 1102.8 (calculated value are as follows: 1102.2)；Theoretical elemental content (%) C56H56Br2N4O2S4: C, 60.86；H, 5.11；N, 5.07；S, 11.60；Actual measurement element contains Measure (%): C, 60.74；H, 5.21；N, 5.14；S, 11.72.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 33: compound IIDDTh-C8The synthesis of PyBr:
IIDDTh-C8The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, is only made using 1,8-, bis- bromooctane For raw material (black solid, yield 90.3%).The molecular ion quality that mass spectral analysis determines are as follows: 1130.8 (calculated value are as follows: 1130.2)；Theoretical elemental content (%) C58H60Br2N4O2S4: C, 61.48；H, 5.34；N, 4.94；S, 11.32；Actual measurement element contains Measure (%): C, 61.55；H, 5.42；N, 4.85；S, 11.12.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 34: compound IIDDTh-C9The synthesis of PyBr:
IIDDTh-C9The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, is only made using 1,9- dibromo nonane For raw material (black solid, yield 93.3%).The molecular ion quality that mass spectral analysis determines are as follows: 1158.8 (calculated value are as follows: 1158.2)；Theoretical elemental content (%) C60H64Br2N4O2S4: C, 62.06；H, 5.56；N, 4.82；S, 11.04；Actual measurement element contains Measure (%): C, 62.15；H, 5.75；N, 4.64；S, 11.01.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 35: compound IIDDTh-C10The synthesis of PyBr:
IIDDTh-C10The synthesis of PyBr and IIDDTh-C4PyBr method is completely the same, only uses 1,10- dibromo-decane As raw material (black solid, yield 91.5%).The molecular ion quality that mass spectral analysis determines are as follows: 1186.8 (calculated value are as follows: 1186.3)；Theoretical elemental content (%) C62H68Br2N4O2S4: C, 62.62；H, 5.76；N, 4.71；S, 10.78；Actual measurement element contains Measure (%): C, 62.78；H, 5.83；N, 4.52；S, 10.66.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 36: compound IIDTh-C4The synthesis of NSB:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- bis- connect thienyl boric acid (590mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, distilled anhydrous with syringe injection 30ml under nitrogen atmosphere Tetrahydrofuran, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, remove Heating reflux reaction 12 hours after Dewar, after being cooled to room temperature, solution obtains black solid by revolving method, extracts dried Then filter revolving is obtained red-black with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Color powdery product IIDDTh-C4Br, then by compound IIDDTh-C4Br (800.0mg, 1.0mmol), dimethylamine hydrochloride (850.0mg, 5.1mmol), Anhydrous potassium carbonate (710.0mg, 5.1mmol), n,N-Dimethylformamide (DMF) 25mL are placed in It is heated to 100 DEG C of 20 hours of reaction in 100mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature revolving and removes solvent, extract drying Then filtering revolving separates (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) with the method that column chromatographs, obtains To black powder solid IIDDTh-C4N, finally by compound IIDDTh-C4N (450.0mg, 0.5mmol), 1,3- propane sulphur Acid lactone (488.0mg, 4.0mmol), anhydrous tetrahydro furan 15mL are placed in 50mL bottle with two necks, are heated to reflux in nitrogen atmosphere It 12 hours, is cooled to room temperature and boils off solvent, filter, filter cake is with 100mL CH2Cl2Washing, drying, obtains black powder product IIDDTh-C4NSB (black solid, 410mg, yield 83.1%).The molecular ion quality that mass spectral analysis determines are as follows: 1034.8 (calculated value are as follows: 1034.3)；Theoretical elemental content (%) C50H58N4O8S6: C, 58.00；H, 5.65；N, 5.41；S, 18.58；It is real Survey constituent content (%): C, 58.12；H, 5.75；N, 5.32；S, 18.50.Above-mentioned analysis the result shows that, the product of acquisition is pre- The product of meter.
Embodiment 37: compound IIDDTh-C5The synthesis of NSB:
IIDDTh-C5The synthesis of NSB and IIDDTh-C4NSB method is completely the same, only uses 1, pentamethylene bromide conduct Raw material (black solid, yield 85.4%).The molecular ion quality that mass spectral analysis determines are as follows: 1062.8 (calculated value are as follows: 1062.3)；Theoretical elemental content (%) C52H62N4O8S6: C, 58.73；H, 5.88；N, 5.27；S, 18.09；Survey constituent content (%): C, 58.75；H, 5.96；N, 5.10；S, 18.01.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 38: compound IIDDTh-C6The synthesis of NSB:
IIDDTh-C6The synthesis of NSB and IIDDTh-C4NSB method is completely the same, only uses the conduct of 1,6- dibromo-hexane Raw material (black solid, yield 87.1%).The molecular ion quality that mass spectral analysis determines are as follows: 1090.8 (calculated value are as follows: 1090.3)；Theoretical elemental content (%) C54H66N4O8S6: C, 59.42；H, 6.10；N, 5.13；S, 17.62；Survey constituent content (%): C, 59.53；H, 5.99；N, 5.02；S, 17.55.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 39: compound IIDDTh-C7The synthesis of NSB:
IIDDTh-C7The synthesis of NSB and IIDDTh-C4NSB method is completely the same, only uses the conduct of 1,7- dibromo-heptane Raw material (black solid, yield 86.8%).The molecular ion quality that mass spectral analysis determines are as follows: 1118.9 (calculated value are as follows: 1118.4)；Theoretical elemental content (%) C56H70N4O8S6: C, 60.08；H, 6.30；N, 5.00；S, 17.18；Survey constituent content (%): C, 59.97；H, 6.12；N, 5.15；S, 17.22.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 40: compound IIDDTh-C8The synthesis of NSB:
IIDDTh-C8The synthesis of NSB and IIDDTh-C4NSB method is completely the same, only uses 1,8-, bis- bromooctane conduct Raw material (black solid, yield 89.6%).The molecular ion quality that mass spectral analysis determines are as follows: 1147.0 (calculated value are as follows: 1146.4)；Theoretical elemental content (%) C58H74N4O8S6: C, 60.70；H, 6.50；N, 4.88；S, 16.76；Survey constituent content (%): C, 60.85；H, 6.39；N, 4.93；S, 16.43.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 41: compound IIDDTh-C9The synthesis of NSB:
IIDDTh-C9The synthesis of NSB and IIDDTh-C4NSB method is completely the same, only uses the conduct of 1,9- dibromo nonane Raw material (black solid, yield 90.1%).The molecular ion quality that mass spectral analysis determines are as follows: 1175.0 (calculated value are as follows: 1174.4)；Theoretical elemental content (%) C60H78N4O8S6: C, 61.30；H, 6.69；N, 4.77；S, 16.36；Survey constituent content (%): C, 61.56；H, 6.79；N, 4.83；S, 16.50.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 42: compound IIDDTh-C10The synthesis of NSB:
IIDDTh-C10The synthesis of NSB and IIDDTh-C4NSB method is completely the same, is only made using 1,10- dibromo-decane For raw material (black solid, yield 90.5%).The molecular ion quality that mass spectral analysis determines are as follows: 1203.0 (calculated value are as follows: 1202.5)；Theoretical elemental content (%) C62H82N4O8S6: C, 61.87；H, 6.87；N, 4.65；S, 15.98；Survey constituent content (%): C, 61.59；H, 6.92；N, 4.71；S, 15.85.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 43: compound IIDPh-C4The synthesis of PyBr:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), phenyl boric acid (300mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), it is placed in 100ml twoport round-bottomed flask, injects the distilled anhydrous tetrahydro furan of 30ml with syringe under nitrogen atmosphere It mutters, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, after removing Dewar Heating reflux reaction 12 hours, after being cooled to room temperature, solution obtained brown solid, extraction dry filter rotation by revolving method It steams, then obtains red-black toner with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Last shape product IIDPh-C4Br, finally by compound IIDPh-C4Br (175.0mg, 0.25mmol), pyridine 20mL are placed in 50mL It is heated to reflux 8 hours in bottle with two necks, in nitrogen atmosphere, is cooled to room temperature, filters, filter cake is with 100mL CH2Cl2Washing is dried It is dry, obtain brown solid 180mg, yield 90.0%.The molecular ion quality that mass spectral analysis determines are as follows: 842.8 (calculated value are as follows: 842.2)；Theoretical elemental content (%) C46H44Br2N4O2: C, 65.41；H, 5.25；N, 6.63；Constituent content (%): C is surveyed, 65.88；H, 5.17；N, 6.19.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 44: compound IIDPh-C5The synthesis of PyBr:
IIDPh-C5The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, only uses 1, pentamethylene bromide conduct Raw material (brown solid, yield 91.2%).The molecular ion quality that mass spectral analysis determines are as follows: 870.8 (calculated values are as follows: 870.2)； Theoretical elemental content (%) C48H48Br2N4O2: C, 66.06；H, 5.54；N, 6.42；Survey constituent content (%): C, 66.14；H, 5.49；N, 6.33.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 45: compound IIDPh-C6The synthesis of PyBr:
IIDPh-C6The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, only uses the conduct of 1,6- dibromo-hexane Raw material (brown solid, yield 89.9%).The molecular ion quality that mass spectral analysis determines are as follows: 898.8 (calculated values are as follows: 898.2)； Theoretical elemental content (%) C50H52Br2N4O2: C, 66.67；H, 5.82；N, 6.22；Survey constituent content (%): C, 66.93；H, 5.77；N, 6.13.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 46: compound IIDPh-C7The synthesis of PyBr:
IIDPh-C7The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, only uses the conduct of 1,7- dibromo-heptane Raw material (brown solid, yield 90.4%).The molecular ion quality that mass spectral analysis determines are as follows: 926.8 (calculated values are as follows: 926.3)； Theoretical elemental content (%) C52H56Br2N4O2: C, 67.24；H, 6.08；N, 6.03；Survey constituent content (%): C, 67.53；H, 6.01；N, 5.84.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 47: compound IIDPh-C8The synthesis of PyBr:
IIDPh-C8The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, only uses 1,8-, bis- bromooctane conduct Raw material (brown solid, yield 90.4%).The molecular ion quality that mass spectral analysis determines are as follows: 954.9 (calculated values are as follows: 954.3)； Theoretical elemental content (%) C54H60Br2N4O2: C, 67.78；H, 6.32；N, 5.86；Survey constituent content (%): C, 67.88；H, 6.55；N, 5.60.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 48: compound IIDPh-C9The synthesis of PyBr:
IIDPh-C9The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, only uses the conduct of 1,9- dibromo nonane Raw material (brown solid, yield 88.2%).The molecular ion quality that mass spectral analysis determines are as follows: 984.9 (calculated values are as follows: 984.3)； Theoretical elemental content (%) C56H64Br2N4O2: C, 68.29；H, 6.55；N, 5.69；Survey constituent content (%): C, 68.40；H, 6.24；N, 5.52.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 49: compound IIDPh-C10The synthesis of PyBr:
IIDPh-C10The synthesis of PyBr and IIDPh-C4PyBr method is completely the same, is only made using 1,10- dibromo-decane For raw material (brown solid, yield 81.2%).The molecular ion quality that mass spectral analysis determines are as follows: 1010.4 (calculated value are as follows: 1010.4)；Theoretical elemental content (%) C58H68Br2N4O2: C, 68.77；H, 6.77；N, 5.53；Constituent content (%): C is surveyed, 68.96；H, 6.54；N, 5.21.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 50: compound IIDPh-C4The synthesis of NSB:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), phenyl boric acid (300mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), it is placed in 100ml twoport round-bottomed flask, injects the distilled anhydrous tetrahydro furan of 30ml with syringe under nitrogen atmosphere It mutters, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, after removing Dewar Heating reflux reaction 12 hours, after being cooled to room temperature, solution obtained black solid, extraction dry filter rotation by revolving method It steams, then obtains red-black toner with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Last shape product IIDDTh-C4Br, then by compound IIDDTh-C4Br (800.0mg, 1.0mmol), dimethylamine hydrochloride (850.0mg, 5.1mmol), Anhydrous potassium carbonate (710.0mg, 5.1mmol), n,N-Dimethylformamide (DMF) 25mL are placed in 100mL twoport In bottle, it is heated to 100 DEG C of 20 hours of reaction in nitrogen atmosphere, is cooled to room temperature revolving and removes solvent, extraction dry filter rotates, Then (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) is separated with the method that column chromatographs, obtains black powder Last shape solid IIDPh-C4N, finally by compound IIDPh-C4N (350.0mg, 0.5mmol), 1,3- propane sultone (488.0mg, 4.0mmol), anhydrous tetrahydro furan 15mL are placed in 50mL bottle with two necks, and it is small that 12 are heated to reflux in nitrogen atmosphere When, it is cooled to room temperature and boils off solvent, filter, filter cake is with 100mL CH2Cl2Washing, drying, obtains black powder product IIDDTh-C4NSB (black solid, 380mg, yield 80.1%).The molecular ion quality that mass spectral analysis determines are as follows: 858.8 (meters Calculation value are as follows: 858.4)；Theoretical elemental content (%) C46H58N4O8S2: C, 64.31；H, 6.81；N, 6.52；S, 7.46；Actual measurement member Cellulose content (%): C, 64.60；H, 6.44；N, 6.41；S, 7.63.Above-mentioned analysis the result shows that, the product of acquisition is estimated production Product.
Embodiment 51: compound IIDPh-C5The synthesis of NSB:
IIDPh-C5The synthesis of NSB and IIDPh-C4NSB method is completely the same, only uses 1, pentamethylene bromide is as former Expect (black solid, yield 85.2%).The molecular ion quality that mass spectral analysis determines are as follows: 886.8 (calculated values are as follows: 886.4)；Reason Argument cellulose content (%) C48H62N4O8S2: C, 64.99；H, 7.04；N, 6.32；S, 7.23；Constituent content (%): C is surveyed, 64.87；H, 7.10；N, 6.24；S, 7.15.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 52: compound IIDPh-C6The synthesis of NSB:
IIDPh-C6The synthesis of NSB and IIDPh-C4NSB method is completely the same, only using 1,6-, bis- bromooctane as former Expect (black solid, yield 86.4%).The molecular ion quality that mass spectral analysis determines are as follows: 914.9 (calculated values are as follows: 914.4)；Reason Argument cellulose content (%) C50H66N4O8S2: C, 65.62；H, 7.27；N, 6.12；S, 7.01；Constituent content (%): C is surveyed, 65.72；H, 7.05；N, 6.14；S, 6.83.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 53: compound IIDPh-C7The synthesis of NSB:
IIDPh-C7The synthesis of NSB and IIDPh-C4NSB method is completely the same, only using 1,7- dibromo-heptane as former Expect (black solid, yield 87.5%).The molecular ion quality that mass spectral analysis determines are as follows: 942.9 (calculated values are as follows: 942.5)；Reason Argument cellulose content (%) C52H70N4O8S2: C, 66.21；H, 7.48；N, 5.94；S, 6.80；Constituent content (%): C is surveyed, 66.48；H, 7.35；N, 5.72；S, 6.82.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 54: compound IIDPh-C8The synthesis of NSB:
IIDPh-C8The synthesis of NSB and IIDPh-C4NSB method is completely the same, only using 1,8-, bis- bromooctane as former Expect (black solid, yield 90.1%).The molecular ion quality that mass spectral analysis determines are as follows: 970.9 (calculated values are as follows: 970.5)；Reason Argument cellulose content (%) C54H74N4O8S2: C, 66.77；H, 7.68；N, 5.77；S, 6.60；Constituent content (%): C is surveyed, 66.68；H, 7.75；N, 5.70；S, 6.47.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 55: compound IIDPh-C9The synthesis of NSB:
IIDPh-C9The synthesis of NSB and IIDPh-C4NSB method is completely the same, only using 1,9- dibromo nonane as former Expect (black solid, yield 93.1%).The molecular ion quality that mass spectral analysis determines are as follows: 999.0 (calculated values are as follows: 998.5)；Reason Argument cellulose content (%) C56H78N4O8S2: C, 67.30；H, 7.87；N, 5.61；S, 6.42；Constituent content (%): C is surveyed, 67.39；H, 7.84；N, 5.56；S, 6.34.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 56: compound IIDPh-C10The synthesis of NSB:
IIDPh-C10The synthesis of NSB and IIDPh-C4NSB method is completely the same, only uses the conduct of 1,10- dibromo-decane Raw material (black solid, yield 87.5%).The molecular ion quality that mass spectral analysis determines are as follows: 1027.0 (calculated value are as follows: 1026.6)；Theoretical elemental content (%) C58H82N4O8S2: C, 67.80；H, 8.04；N, 5.45；S, 6.24；Survey constituent content (%): C, 67.94；H, 8.06；N, 5.37；S, 6.10.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 57: compound IIDTTh-C4The synthesis of PyBr:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4 (6), 1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere It is heated to 105 DEG C after first stirring at normal temperature 4 hours to react 14 hours, is cooled to room temperature for solution and red is obtained by revolving method Solid, extraction dry filter revolving, then separates (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) with column chromatography method Obtain red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- tri- connect thiophene boron Sour (880mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, distilled anhydrous with syringe injection 30ml under nitrogen atmosphere Tetrahydrofuran, then liquid nitrogen progress Degas operation in 15 minutes is added in device Dewar outside reaction flask under vacuum condition, removes Dewar Heating reflux reaction 12 hours afterwards, after being cooled to room temperature, solution obtains black solid, extraction dry filter rotation by revolving method It steams, then obtains red-black toner with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Last shape product IIDTTh-C4Br, finally by compound IIDTTh-C4Br (850.0mg, 0.27mmol), pyridine 20mL are placed in It is heated to reflux 8 hours in 50mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature, filters, filter cake is with 100mL CH2Cl2Washing, Drying, obtains black solid, 300mg, yield 91.0%.The molecular ion quality that mass spectral analysis determines are as follows: 1180.3 (calculated values Are as follows: 1180.0)；Theoretical elemental content (%) C58H46Br2N4O2S6: C, 58.88；H, 3.92；N, 4.74；S, 16.26；Actual measurement member Cellulose content (%): C, 59.10；H, 3.82；N, 4.50；S, 16.31.Above-mentioned analysis the result shows that, the product of acquisition is estimated Product.
Embodiment 58: compound IIDTTh-C6The synthesis of PyBr:
IIDTTh-C6The synthesis of PyBr and IIDTTh-C4PyBr method is completely the same, is only made using 1,6- dibromo-hexane For raw material (black solid, yield 90.0%).The molecular ion quality that mass spectral analysis determines are as follows: 1236.4 (calculated value are as follows: 1236.1)；Theoretical elemental content (%) C62H54Br2N4O2S6: C, 60.09；H, 4.39；N, 4.52；S, 15.52；Actual measurement element contains Measure (%): C, 60.00；H, 4.53；N, 4.38；S, 15.47.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 59: compound IIDTTh-C8The synthesis of PyBr:
IIDTTh-C8The synthesis of PyBr and IIDTTh-C4PyBr method is completely the same, is only made using 1,8-, bis- bromooctane For raw material (black solid, yield 85.4%).The molecular ion quality that mass spectral analysis determines are as follows: 1292.6 (calculated value are as follows: 1292.2)；Theoretical elemental content (%) C66H62Br2N4O2S6: C, 61.19；H, 4.82；N, 4.33；S, 14.85；Actual measurement element contains Measure (%): C, 61.52；H, 4.90；N, 4.38；S, 14.40.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 60: compound IIDTTh-C4The synthesis of NSB:
The compound 6- bromo bioxindol (Poly.Chem, 2013,4,1836-1841) that will be synthesized according to document, (2.0g, 4.8mmol), Isosorbide-5-Nitrae-dibromobutane (9.3g, 38.1mmol), petroleum ether cleaning ultrasound cross sodium hydride (1.4g, 60%, 38.1mmol), anhydrous n,N-Dimethylformamide (DMF) 100mL is placed in 250mL bottle with two necks, in nitrogen atmosphere often first Warm stirring is heated to 105 DEG C after 4 hours and reacts 14 hours, is cooled to room temperature for solution and obtains red admittedly by revolving method Body, extraction dry filter revolving, is then obtained with column chromatography method separation (silica gel, methylene chloride/petroleum ether, volume ratio 1:1) Red powder product IIDBr-C4Br, later by compound IIDBr-C4Br (500mg, 0.7mmol), 2- tri- connect thienyl boric acid (880mg, 2.8mmol), tris(dibenzylideneacetone) dipalladium (37.0mg, 0.04mmol), three (o-methyl-phenyl) phosphines (35.0mg, 0.1mmol), is placed in 100ml twoport round-bottomed flask, distilled anhydrous with syringe injection 30ml under nitrogen atmosphere Tetrahydrofuran, then liquid nitrogen 15 minutes nitrogen replacement operators of progress are added in device Dewar outside reaction flask under vacuum condition, remove Heating reflux reaction 12 hours after Dewar, after being cooled to room temperature, solution obtains black solid by revolving method, extracts dried Then filter revolving is obtained red-black with column chromatography method separation (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) Color powdery product IIDTTh-C4Br, then by compound IIDTTh-C4Br (850.0mg, 1.0mmol), dimethylamine hydrochloride (850.0mg, 5.1mmol), Anhydrous potassium carbonate (710.0mg, 5.1mmol), n,N-Dimethylformamide (DMF) 25mL are placed in It is heated to 100 DEG C of 20 hours of reaction in 100mL bottle with two necks, in nitrogen atmosphere, is cooled to room temperature revolving and removes solvent, extract drying Then filtering revolving separates (silica gel, methylene chloride/methanol/triethylamine, volume ratio 100:2:1) with the method that column chromatographs, obtains To black powder solid IIDTTh-C4N, finally by compound IIDTTh-C4N (500.0mg, 0.5mmol), 1,3- propane sulphur Acid lactone (488.0mg, 4.0mmol), anhydrous tetrahydro furan 15mL are placed in 50mL bottle with two necks, are heated to reflux in nitrogen atmosphere It 12 hours, is cooled to room temperature and boils off solvent, filter, filter cake is with 100mL CH2Cl2Washing, drying, obtains black powder product IIDTTh-C4NSB (black solid, 430mg, yield 84.0%).The molecular ion quality that mass spectral analysis determines are as follows: 1196.5 (calculated value are as follows: 1196.2)；Theoretical elemental content (%) C58H60N4O8S8: C, 58.17；H, 5.05；N, 4.68；S, 21.42；It is real Survey constituent content (%): C, 58.12；H, 5.12；N, 4.32；S, 21.50.Above-mentioned analysis the result shows that, the product of acquisition is pre- The product of meter.
Embodiment 61: compound IIDTTh-C6The synthesis of NSB:
IIDTTh-C6The synthesis of NSB and IIDTTh-C4NSB method is completely the same, only uses the conduct of 1,6- dibromo-hexane Raw material (black solid, yield 87.3%).The molecular ion quality that mass spectral analysis determines are as follows: 1252.7 (calculated value are as follows: 1252.3)；Theoretical elemental content (%) C62H68Br2N4O2S6: C, 59.40；H, 5.47；N, 4.47；S, 20.46；Actual measurement element contains Measure (%): C, 59.62；H, 5.52；N, 4.19；S, 20.33.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 62: compound IIDTTh-C8The synthesis of NSB:
IIDTTh-C8The synthesis of NSB and IIDTTh-C4NSB method is completely the same, only uses 1,8-, bis- bromooctane conduct Raw material (black solid, yield 91.2%).The molecular ion quality that mass spectral analysis determines are as follows: 1308.7 (calculated value are as follows: 1308.3)；Theoretical elemental content (%) C66H76Br2N4O2S6: C, 60.52；H, 5.85；N, 4.28；S, 19.58；Actual measurement element contains Measure (%): C, 60.61；H, 5.75；N, 4.06；S, 19.66.Above-mentioned analysis the result shows that, the product of acquisition is estimated product.
Embodiment 63:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IID-C6PyBr/Al]
Successively spin coating anode modification layer PEDOT:PSS, thickness are about 30nm in the glass substrate for be coated with ito anode；It is living Property layer PTB7:PC71BM, thickness are about 90nm, embellishing cathode interface layer IID-C6PyBr (preparation method: utilizing spin coating instrument, Concentration is 0.8mgmL-1IID-C6The methanol solution of PyBr rotates 1min under the revolving speed of 2000r/min), thickness is about 5nm； Evaporating Al cathode, thickness are about 100nm, and it is 5 × 10 that pressure is kept during vapor deposition-6Pa.The device open-circuit voltage is 0.75V, short-circuit current density 16.10mAcm-2, fill factor 63.7%, being computed incident photon-to-electron conversion efficiency is 7.69%.
Embodiment 64:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IID-C6NSB/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IID-C6NSB replaces IID-C6PyBr.The device Open-circuit voltage is 0.75V, short-circuit current density 16.44mAcm-2, fill factor 65.0%, being computed incident photon-to-electron conversion efficiency is 8.02%.
Embodiment 65:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDTh-C6PyBr/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDTh-C6PyBr replaces IID-C6PyBr.It should Device open-circuit voltage is 0.76V, short-circuit current density 16.75mAcm-2, fill factor 65.6%, be computed photoelectric conversion effect Rate is 8.35%.
Embodiment 66:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDTh-C6NSB/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDTh-C6NSB replaces IID-C6PyBr.The device Part open-circuit voltage is 0.75V, short-circuit current density 16.90mAcm-2, fill factor 71.6% is computed incident photon-to-electron conversion efficiency It is 9.08%.
Embodiment 67:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDPh-C6PyBr/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDPh-C6PyBr replaces IID-C6PyBr.It should Device open-circuit voltage is 0.75V, short-circuit current density 16.25mAcm-2, fill factor 64.2%, be computed photoelectric conversion effect Rate is 7.82%.
Embodiment 68:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDPh-C6NSB/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDPh-C6NSB replaces IID-C6PyBr.The device Part open-circuit voltage is 0.75V, short-circuit current density 16.62mAcm-2, fill factor 65.9% is computed incident photon-to-electron conversion efficiency It is 8.21%.
Embodiment 69:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDDTh-C6PyBr/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDDTh-C6PyBr replaces IID-C6PyBr.It should Device open-circuit voltage is 0.75V, short-circuit current density 16.45mAcm-2, fill factor 66.2%, be computed photoelectric conversion effect Rate is 8.17%.
Embodiment 70:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDDTh-C6NSB/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDDTh-C6NSB replaces IID-C6PyBr.It should Device open-circuit voltage is 0.76V, short-circuit current density 16.70mAcm-2, fill factor 67.2%, be computed photoelectric conversion effect Rate is 8.53%.
Embodiment 71:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDTTh-C6PyBr/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDTTh-C6NSB replaces IID-C6PyBr.It should Device open-circuit voltage is 0.76V, short-circuit current density 16.55mAcm-2, fill factor 66.3%, be computed photoelectric conversion effect Rate is 8.34%.
Embodiment 72:
Photovoltaic device [ITO/PEDOT:PSS/PTB7:PC71BM/IIDTTh-C6NSB/Al]
According to IID-C6The device fabrication process of PyBr, step is identical, uses IIDTTh-C6NSB replaces IID-C6PyBr.It should Device open-circuit voltage is 0.76V, short-circuit current density 16.66mAcm-2, fill factor 67.1%, be computed photoelectric conversion effect Rate is 8.49%.

Claims (4)

1. a kind of using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer, it is characterised in that: bioxindol spreads out The structural formula of biology is as follows,
Wherein, n is 4 to 10 integer, and R1 is two kinds of groups of structural formula pyridiniujm as follows or dimethylamine sulfonate inner salt, R2 It is H, thiophene, two company's thiophene, three company's thiophene or phenyl ring；
2. it is as described in claim 1 a kind of using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer, It is characterized in that: shown in one of the structural formula of bioxindol derivative is following,
3. it is as claimed in claim 1 or 2 a kind of using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer, It is characterized by: device architecture is sequentially that the ito anode being attached on transparent glass, anode modification layer, active layer, bioxindol spread out Biological-cathode interface-modifying layer and metal Al cathode.
4. it is as claimed in claim 3 a kind of using bioxindol derivative as the polymer photovoltaic cell of embellishing cathode interface layer, It is characterized in that: being using PEDOT-PSS as anode modification layer, take mass ratio as the PTB7:PC of 1.8~2.2:2.7~3.371BM is Active layer.
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Families Citing this family (4)

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CN105977493B (en) * 2016-07-14 2019-04-05 宁德时代新能源科技股份有限公司 Conductive agent, preparation method thereof and lithium ion battery containing conductive agent
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103304782A (en) * 2013-05-14 2013-09-18 上海交通大学 Conjugated polymer with N-acyl-substituted isoindigo radical and preparation method of conjugated polymer
CN103865041A (en) * 2012-12-12 2014-06-18 海洋王照明科技股份有限公司 Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof
KR20150002216A (en) * 2013-06-28 2015-01-07 광주과학기술원 Isoindigo derivative based compounds, methods for manufacturing the same, and soluble-processed organic photovolatic devices comprising the same
CN104497279A (en) * 2014-12-05 2015-04-08 华南理工大学 Donor-receptor type organic semiconductor material with removable group anthracene unit and preparation method of donor-receptor type organic semiconductor material

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8809484B2 (en) * 2012-12-27 2014-08-19 Xerox Corporation Extended isoindigo polymers and semiconductor compositions

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103865041A (en) * 2012-12-12 2014-06-18 海洋王照明科技股份有限公司 Conjugated polymer containing bioxindol-dibenzothiophenebenzodithiophene and preparation method and application thereof
CN103304782A (en) * 2013-05-14 2013-09-18 上海交通大学 Conjugated polymer with N-acyl-substituted isoindigo radical and preparation method of conjugated polymer
KR20150002216A (en) * 2013-06-28 2015-01-07 광주과학기술원 Isoindigo derivative based compounds, methods for manufacturing the same, and soluble-processed organic photovolatic devices comprising the same
CN104497279A (en) * 2014-12-05 2015-04-08 华南理工大学 Donor-receptor type organic semiconductor material with removable group anthracene unit and preparation method of donor-receptor type organic semiconductor material

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