CN108218887A - A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application - Google Patents

A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application Download PDF

Info

Publication number
CN108218887A
CN108218887A CN201710994403.6A CN201710994403A CN108218887A CN 108218887 A CN108218887 A CN 108218887A CN 201710994403 A CN201710994403 A CN 201710994403A CN 108218887 A CN108218887 A CN 108218887A
Authority
CN
China
Prior art keywords
benzheterocycle
molecular material
fluorine atom
conjugated molecular
material based
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201710994403.6A
Other languages
Chinese (zh)
Inventor
应磊
钟文楷
黄飞
曹镛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201710994403.6A priority Critical patent/CN108218887A/en
Publication of CN108218887A publication Critical patent/CN108218887A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • 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
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electromagnetism (AREA)
  • Photovoltaic Devices (AREA)

Abstract

The invention discloses a kind of conjugated molecular materials based on fluorine atom substitution benzheterocycle and preparation method and application.The conjugated molecular material is receptor Donor acceptor type structure, wherein, receptor unit is jointly built-up for the benzheterocycle structure and electrophilic dye units replaced using fluorine atom.The conjugated molecular material has the characteristics such as absorption spectrum is easy to regulate and control with molecular entergy level, photo absorption performance is strong, electron mobility is high, has great application prospect in organic photovoltaic cell and organic field effect tube field.

Description

A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method thereof With application
Technical field
The invention belongs to organic photoelectrical material technical fields, and in particular to a kind of being total to based on fluorine atom substitution benzheterocycle The preparation of molecular conjugate and its application in organic photoelectric technical field.
Background technology
Organic photovoltaic cell (Organic Photovoltaics) compared to traditional silica-based solar cell have low cost, The advantages that large area, flexibility, frivolous, solution processable and as the new primary study object of scientists.Past is over more than 20 years, Researcher prepares by synthesizing a large amount of organic electron materials, and with fullerene derivate (PCBM) blending as photoactive layer Into solar cell device, at present the Laboratory efficiencies of individual layer organic photovoltaic cell have reached 10.3% [Nat.Commun., 5 (2014) 5293], and the energy transformation ratio of lamination organic photovoltaic cell also reaches 10.6% [Nat.Commun., 4 (2013) 1446], therefore, organic photovoltaic cell has bright commercial promise.However, the shortcomings that fullerene derivate, is mainly reflected in： (1) in the mass content of photoactive layer generally more than 50%, but absorb in the wave-length coverage of 500-900nm it is very weak, no Conducive to the short-circuit current density for further improving organic photovoltaic cell；(2) microcosmic crystalline region is easily spontaneously formed, is unfavorable for photolytic activity The microscopic appearance of layer is steady in a long-term, and the energy transformation ratio of organic photovoltaic cell is caused to be decayed quickly；(3) very high synthesis is with changing Property cost and costliness price, be unfavorable for further reduce organic photovoltaic cell production cost.
So in recent years, research direction is gradually turned to non-fullerene acceptor material by organic photovoltaic cell field, is passed through The suitable electron material of selection is blended and optimizes with non-fullerene acceptor material, and non-fullerene acceptor material gradually shows Go out the electron acceptor energy more more excellent than fullerene derivate.A large amount of acceptor material is the structure based on acid imide at present, From initial based on naphthalimide or imido polymer, such as commercialized N2200 polymer develops into based on acyl The small molecule material of imines various structures, the seminar of the Alex K.-Y.Jen and A.Jenekhe of University of Washington close respectively Into acceptor material [Adv.Mater., 26 (2014) 5708- with the big steric hindrance in space based on PDI and BFI macrocyclic structures 5714；Macromolecules, 48 (2015) 1759-1766], electricity conversion respectively reaches 6.72% and 8.52%；Brother The researchs such as the Nuckolls of rival Asia university have been combined into 2-4 PDI and toroidal molecule, the energy transformation ratio with PTB7-Th blendings Have reached 8.27% [Nat.Commun., 6 (2015) 8242.] after certification；The Kilwon Cho seminar of South Korea also synthesizes The small molecule receptor material with three-dimensional structure that spiro fluorene is connect with four PDI, can with polymer P V4T2FBT blending efficiency To reach 5.98% [Adv.Mater., 28 (2016), 69-76].At home, the Xiao Wei researchs that account for of Beijing University have been combined into based on drawing Up to the IEIC small molecules for saving 1,4-Dithiapentalene or dithieno indacene 1,4-Dithiapentalene and the dye units of the structure containing malononitrile and ITIC [Adv.Mater., 27 (2015) 1170-1174], by itself and PTB7-Th, and by the use of PDIN as interface optimization, obtains energy It is respectively 6.3% and 7.52% to measure conversion ratio；The bright seminar of Sun Yan of Beijing Institute of Aeronautics introduces sulphur atom synthesis on the big rings of PDI Itself and polymer P DBT-T1 are blended to obtain efficiency as 7.16% [J.Am.Chem.Soc., 137 (2015) by SdiPBI-S molecules 11156-11162]；The Yan He seminar of Hong Kong University of Science and Thchnology studies what is be combined into using the IEIC materials for accounting for Xiao Wei groups with them Solar cell prepared by donor material PffT2-FTAZ-2DT blendings, efficiency reach 7.3% [Adv.Mater.2015,27, 7299-7304]。
In numerous non-fullerene acceptors, contain the small molecule of diazosulfide unit as acceptor material also gradually by Extensive concern, device prepared by the photoactive layer that is blended therewith using poly- (3- hexyl thiophenes) with fullerene derivate than being blended Show higher energy transformation ratio [J.Am.Chem.Soc., 137 (2015) 898-904；Energy Environ.Sci.,8 (2015)3215-3221].Compared with diazosulfide, if the hydrogen on 5 on its phenyl ring or 6 carbon atoms is substituted by fluorine original Son can enhance intermolecular accumulation while promote the electronics push-and-pull action of intramolecular, so as to improve the carrier transport of polymer Performance [J.Am.Chem.Soc., 134 (2012) 14932-14944].So it is further promoted this containing diazosulfide unit Acceptor material performance, fluorine substitution be a kind of highly effective means.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to it provides a kind of based on fluorine atom substitution benzheterocycle Conjugated molecular material.The conjugated molecular material is acceptor-donor-receptor type structure, wherein, receptor unit is takes using fluorine atom The benzheterocycle structure and electrophilic dye units in generation are jointly built-up.
The present invention also aims to provide a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle Preparation method.
The present invention also aims to provide a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle Application.There is the conjugated molecular material absorption spectrum to be easy to regulate and control with molecular entergy level, photo absorption performance is strong, electron mobility High characteristic has great application prospect in organic photovoltaic cell and organic field effect tube field.
The purpose of the present invention is achieved through the following technical solutions.
A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle, which is characterized in that chemical structural formula is as follows：
In formula, Ar1 and Ar2 are electron unit, and Ar3 is electrophilic unit；X1、X2、X3And X4Be independently chosen from H or F, and X1、X2、X3And X4It is asynchronously H；
Electron unit Ar1 is any one of following structural formula：
Electron unit Ar2 is heterocycle structure, is any one of following structural formula：
Wherein, R be hydrogen, C1-C30 alkyl or be more than one carbon atom by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, Amino, carbonyl, carboxyl, nitro, phenyl or thienyl substitution C1-C30 alkyl or for more than one hydrogen atom by halogen atom Substituted C1-C30 alkyl；
Electrophilic unit Ar3 is molecular structure of dye, is any one of following chemical structural formula：
In formula, symbol " * " represents structure and the doubly linked positions of molecule C=C.
It is further preferred that a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle replaces for a fluorine Object, in formula, X1For F, X2、X3And X4It is H；Or X2For F, X1、X3And X4It is H.
It is further preferred that a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle replaces for difluoro Object, in formula, X1And X2It is F, X3And X4It is H；Or X1And X3It is F, X2And X4It is H；Or X1And X4It is F, X2And X3 For H；Or X2And X3It is F, X1And X4It is H.
It is further preferred that a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle replaces for trifluoro Object, in formula, X1、X2And X3Equal F, X4For H；Or X1、X2And X4It is F, X3For H.
It is further preferred that a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle replaces for tetrafluoro Object, in formula, X1、X2、X3And X4Equal F.
In the conjugated molecular material based on fluorine atom substitution benzheterocycle of the present invention, electron unit Ar1 is in molecule Center, X1、X2、X3And X4It is independently chosen from H or F, and X1、X2、X3And X4It is asynchronously H；Meanwhile use different Ar1, Ar2 And Ar3 moiety combinations, thus it is possible to vary the Intramolecular electron transfer effect of material regulates and controls absorbent properties, the molecule energy of polymer Grade, carrier mobility etc.；And for the adjustment of the Ar1 containing R side groups or Ar2 or Ar3 groups, it can effectively control material Solubility realizes the Morphological control of material film.This is conducive in the performance for improving the organic electro-optic device based on the material.
The method for preparing a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle described in any one of the above embodiments, packet Include following steps：
(1) X will be contained1、X2With Ar2 to halogenated benzheterocycle -4- formaldehyde, containing X3、X4With Ar2 to halogenated benzheterocycle -4- Formaldehyde and Ar1 containing double alkyl tin groups are dissolved in organic solvent, and by Stille coupling reactions, synthesis both sides end group is aldehyde The acceptor-donor of base-receptor type intermediate product；
(2) both sides end group is dissolved in for acceptor-donor-receptor type intermediate product of aldehyde radical with Ar3 unit molecules organic molten It in agent, is reacted by Knoevenagel, obtains the conjugated molecular material based on fluorine atom substitution benzheterocycle.
Further, in step (1), containing X1、X2With Ar2 to halogenated benzheterocycle -4- formaldehyde and containing X3、X4With Ar2 pairs The mole ratio of the integral molar quantity of halogenated benzheterocycle -4- formaldehyde and the Ar1 containing double alkyl tin groups are 2.5~3：1.
Further, in step (1), containing X1、X2With Ar2 to halogenated benzheterocycle -4- formaldehyde and containing X3、X4With Ar2 pairs The molar ratio of halogenated benzheterocycle -4- formaldehyde is 1：1.
Further, in step (1), the Stille coupling reactions carry out under atmosphere of inert gases.
Further, in step (1), the organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, chloroform or tetrahydrochysene Furans.
Further, in step (1), the temperature of the Stille coupling reactions is 80-110 DEG C, reaction time 24-48 Hour.
Further, in step (2), the both sides end group is the acceptor-donor-receptor type intermediate product and Ar3 of aldehyde radical The molar ratio of unit molecule is 1:10, and add in the alkali molecules that molar equivalent is 10%.
Further, in step (2), the alkali molecules include pyridine, piperidines or triethylamine.
Further, in step (2), the organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, chloroform or tetrahydrochysene Furans.
Further, in step (2), the Knoevenagel reactions carry out under atmosphere of inert gases.
Further, in step (2), the temperature of the Knoevenagel reactions is 50-60 DEG C, reaction time 50- 120min。
A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle described in any one of the above embodiments is preparing organic light Application in the active layer of electrical part, by being replaced based on fluorine atom, the conjugated molecular material of benzheterocycle and Donor compound are molten It is formed and is dissolved in organic solvent, the active layer of organic electro-optic device is made up of solution processing method.
Further, the quality of the conjugated molecular material and Donor compound based on fluorine atom substitution benzheterocycle Than being 0~1.5:1.
Further, the organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, chloroform, tetrahydrofuran and methyl One or more of tetrahydrofuran.
Further, the thickness of the active layer is 5nm~3 μm.
After the active layer of organic electro-optic device uses the conjugated molecular material based on fluorine atom substitution benzheterocycle to prepare, On the active layer of preparation be deposited one layer of metal electrode, wherein, between active layer and substrate and active layer and metal electrode, activity Charge transport layer can be embedded in enhance the performance of the photoelectric device between layer and substrate or between active layer and metal electrode, be based on Organic electro-optic device prepared by the conjugated molecular material mainly is led with organic solar batteries and organic field effect tube by application Domain.
Compared with prior art, the invention has the advantages that and advantageous effect：
The present invention introduces fluorine atom in conjugated molecule structure, on the one hand, fluorine atom has strong electronegativity in itself, effectively promotees Into Intramolecular electron transfer；On the other hand, fluorine atom can be with the sulphur atom or hydrogen atom on adjacent group or on adjacent molecule Intramolecule or the non-binding effect of outside are formed, realizes that molecule has good flatness and rigidity, is conducive to promote molecule Carrier transmission characteristics.
Description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of conjugated molecular material IFBR-p prepared by embodiment 2；
Fig. 2 is the carbon-13 nmr spectra figure of conjugated molecular material IFBR-p prepared by embodiment 2；
Fig. 3 is the Enantiomeric excess figure of conjugated molecular material IFBR-p prepared by embodiment 2；
Fig. 4 is the mass spectrum of nuclear magnetic resonance figure of conjugated molecular material IFBR-p prepared by embodiment 2；
Fig. 5 is the nuclear magnetic resonance spectroscopy pair of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 Than figure；
The thermogravimetric curve that Fig. 6 is conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 compares Figure；
The differential scanning calorimetry that Fig. 7 is conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 is bent Line comparison diagram；
Fig. 8 is following for the electro-chemical test of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 Ring volt-ampere curve comparison diagram；
The absorption spectrum that Fig. 9 is conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 compares Figure；
Figure 10 is the solar cell of conjugated molecular material IFBR-p and IFBR-d prepared based on embodiment 2 and embodiment 3 VA characteristic curve comparison diagram.
Specific embodiment
In order to better understand the content of the present invention, the present invention is made by specific embodiment and attached drawing again below further Illustrate, but implementation of the invention and protection domain are without being limited thereto.
Embodiment 1
Based on indacene 1,4-Dithiapentalene, 5,6- the fluorobenzene simultaneously conjugated molecular material of [d] [1,2,5] thiadiazoles and rhodanine The synthesis of (abbreviation IffBR)
Synthetic route is as follows：
The preparation of bromo- bis- fluoro- 7- methylbenzenes [c] [1,2,5] thiadiazoles (compound 1) of 5,6- of 4-
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by bromo- 5,6- difluorobenzenes [c] [1,2, the 5] thiadiazoles of 4- (1.0g, 4.0mmol) is dissolved in 50mL tetrahydrofurans, is added dropwise lithium diisopropylamine (12mL, 2.0Min THF), and- 1h is stirred at 78 DEG C.Then iodomethane (1.2g, 8.0mmol) is added in reaction mixture, reaction unit is restored to room temperature, Reaction stirring 8 hours.After reaction, reaction is quenched with water and is poured into water, and extracted with dichloromethane, anhydrous magnesium sulfate Dry, vacuum distillation removes solvent.Crude product passed through silicagel column and further purified, and obtained 0.8g white solids.Yield 75% 。1H NMR(500MHz,CDCl3) δ (ppm) 2.65 (dd, J=4.5,2.6Hz, 3H)13C NMR(126MHz,CDCl3)δ(ppm) 153.29,153.13,152.26,152.12,151.24,151.08,150.97,150.89,150.23,150.08,149.64, 149.60,116.17,116.04,96.66,96.64,96.49,96.47,10.49,10.47,10.45.
The preparation of the bromo- 7- of 4- (two bromomethyls) -5,6- difluorobenzenes [c] [1,2,5] thiadiazoles (compound 3)
Under argon atmospher, in 100mL two-mouth bottles, bromo- 5,6-, bis- fluoro- 7- methylbenzenes [c] [1,2, the 5] thiadiazoles of 4- (0.5g, 1.9mmol), N- bromo-succinimides (1.4g, 7.6mmol) are dissolved in four with benzoyl peroxide (0.23g, 0.94mmol) In chlorination carbon (20mL).By two-mouth bottle as in oil bath, be heated to 90 DEG C and maintain 8 hours.After reaction, reaction solution is fallen Enter in water, and extracted with dichloromethane, anhydrous magnesium sulfate drying, vacuum distillation removes solvent.Crude product passed through silicagel column into One step purifies, and obtains 0.54g white solids.Yield 43%.1H NMR(500MHz,CDCl3) δ (ppm) 7.33 (d, J=1.4Hz, 1H).13C NMR(126MHz,CDCl3)δ(ppm)152.56,152.41,150.51,150.36,149.84,146.26, 146.21,118.78,118.70,102.20,102.18,102.03,102.01,23.91,23.88,23.85.
The preparation of bromo- 5,6- difluoros benzo [c] [1,2,5] thiadiazoles -4- formaldehyde (compound 4) of 7-
Under argon gas atmosphere, in 100mL two-mouth bottles, by the bromo- 7- of 4- (two bromomethyls) -5,6- difluorobenzenes [c] [1,2,5] thiophene Diazole (0.5g, 1.2mmol) is dissolved in 15mL formic acid, and reaction unit is increased to 90 DEG C, reacts 6h.It after reaction, will be anti- Device is answered to restore to room temperature, after formic acid is removed, crude product passed through silicagel column and further purifies, and obtained 0.3g yellow solids. Yield 88%.1H NMR(500MHz,CDCl3)δ(ppm)10.76(s,1H).13C NMR(126MHz,CDCl3)δ(ppm) 184.02,183.99,183.98,183.96,157.47,157.33,155.26,155.11,152.50,152.35,150.43, 150.35,150.32,150.28,146.96,146.91,112.99,112.94,107.58,107.56,107.41, 107.39.19F NMR(471MHz,CDCl3) δ (ppm) -120.38 (d, J=18.7Hz), -128.64 (d, J=18.7Hz)
7,7'- (two indeno [1,2-B of (4- hexyls the phenyl) -4,9- dihydro-s- of 4,4,9,9- tetra- benzos：5,6-B'] two thiophenes Two diyls of fen -2,7-) bis- (5,6- difluoros benzo [c] [1,2,5] thiadiazoles -4- formaldehyde) (compounds 5) preparation
Under argon gas atmosphere, bromo- 5,6- difluoros benzo [c] [1,2, the 5] thiadiazoles -4- formaldehyde (180mg, 0.65mmol) of 7-, 2,7- bis- (tin trimethyl) -4,9- dihydros -4,4,9,9- four (4- hexyls phenyl)-s- indenos not [1,2-b：5,6-b'] Dithiophene (345mg, 0.28mmol) and Pd (PPh3)4(tetrakis triphenylphosphine palladium, 32mg, 0.028mmol) is added in two-mouth bottle, dissolving In the toluene of 15mL, reaction unit is increased into temperature to 110 DEG C, is reacted 48 hours.After reaction, after toluene moves, Crude product passed through silicagel column and further purified, and obtained 225mg red solids.Yield：62%.1H NMR(500MHz, CDCl3) δ (ppm) 10.72 (s, 2H), 8.45 (s, 2H), 7.65 (s, 2H), 7.25 (d, J=8.2Hz, 8H), 7.12 (d, J= 8.2Hz, 8H), 2.63-2.53 (m, 8H), 1.60 (dt, J=15.4,7.6Hz, 8H), 1.39-1.23 (m, 25H), 0.87 (t, J =6.6Hz, 12H)13C NMR(126MHz,CDCl3)δ(ppm)183.99,158.63,158.49,157.47,156.46, 156.32,154.94,148.90,148.84,148.68,148.62,148.50,148.44,146.70,146.56,142.14, 141.26,136.06,134.38,134.36,134.32,134.30,129.76,129.67,128.73,127.97,120.63, 120.56,118.88,110.64,110.59,63.37,35.71,31.85,31.47,29.27,22.73,14.23.
(5Z, 5'Z) -5,5-'- (((4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2-B： 5,6b'] Dithiophene -2,7- diyl) bis- (5,6- difluoro benzo [c] [1,2,5] thiadiazoles -7,4- diyls)) it is bis- that (methyl joins penta 2 Alkene)) preparation of bis- (3- ethyl -2- Thioxothiazolidin -4- ketone) (abbreviation IffBR)
Under argon atmosphere, by 7,7'- (4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2- B：5,6-B'] two diyls of Dithiophene -2,7-) bis- (5,6- difluoros benzo [c] [1,2,5] thiadiazoles -4- formaldehyde) (150mg, 0.115mmol), 3- ethyls rhodanine (186mg, 1.15mmol) is added in two-mouth bottle, is dissolved in the chloroform of 20mL.It will be anti- Device is answered to be warming up to 60 DEG C, is reacted 50 minutes.After reaction, after reaction dissolvent is removed, crude product passed through silicagel column into One step purifies, and obtains 50mg red solids.Yield：27%.
1H NMR(500MHz,CDCl3) δ (ppm) 8.37 (s, 2H), 8.20 (s, 2H), 7.62 (s, 2H), 7.24 (d, J= 8.4Hz, 8H), 7.11 (d, J=8.4Hz, 8H), 4.23 (q, J=7.2Hz, 4H), 2.62-2.52 (m, 8H), 1.64-1.55 (m, 8H), 1.38-1.25 (m, 30H), 0.86 (t, J=6.9Hz, 12H)13C NMR(126MHz,CDCl3)δ(ppm) 194.62,167.75,157.34,154.76,148.74,148.68,148.56,148.48,147.80,147.74,142.05, 141.41,136.00,134.73,134.67,129.35,128.70,128.00,120.50,118.68,117.13,117.03, 110.41,110.32,63.34,40.14,35.72,31.86,31.48,29.29,22.74,14.24,12.47.19F NMR (471MHz,CDCl3) δ (ppm) -124.03 (d, J=15.5Hz), -128.17 (d, J=15.4Hz) .MS (MALDI-TOF) m/ z:cacld for C88H84F4N6O2S8,1588.44；found,1588.354.
Embodiment 2
Based on indacene 1,4-Dithiapentalene, 5- fluorobenzene, simultaneously [d] [1,2,5] thiadiazoles and rhodanine conjugated molecular material be (referred to as IFBR-p synthesis)
Synthetic route is as follows：
The preparation of the fluoro- 3- methylbenzenes -1,2- diamines (compound 6) of 5-
Under argon gas atmosphere, in two mouthfuls of round-bottomed flasks of the 250mL equipped with reflux condenser, the fluoro- 3- methyl -2- of 5- are added in Nitroaniline (5.0g, 29.4mmol) simultaneously adds in 50ml ethyl alcohol and makes its dissolving, while add in Fe powder (8.2g, 147mmol), so Reaction unit is positioned in oil bath pan afterwards, is warming up to 80 DEG C.Be then slowly added into the diluted HCl of use 30mL ethyl alcohol (31mL, 12M).Reaction reflux 8 hours, and cool the temperature to room temperature.Reaction solution is poured into cold NaOH aqueous solutions, ethyl acetate extraction It takes, anhydrous magnesium sulfate drying.Vacuum distillation removes solvent, obtains 3.9g brown oils.Obtained crude product need not be into traveling The purification of one step directly carries out next step reaction.
The preparation of fluoro- 4- methyl benzo [d] [1,2,5] thiadiazoles (compound 7) of 6-
Under argon gas atmosphere, in two mouthfuls of round-bottomed flasks of the 250mL equipped with reflux condenser, the fluoro- 3- methylbenzenes of addition 5-- 1,2- diamines (3.90g, 27.80mmol), and add in 40ml pyridines and make its dissolving.Reaction unit is positioned in ice bath (0 DEG C) stir 30 minutes, thionyl chloride (9.92g, 83.4mmol) is added dropwise in reaction unit.Then round-bottomed flask is put into Temperature of speaking slowly in oil bath pan rises to 60 DEG C, and reaction is for 24 hours.After reaction, reaction mixture is poured into water, that dichloromethane Alkane extracts.Oil phase is dried with anhydrous magnesium sulfate, vacuum distillation removes solvent.Crude product passed through silicagel column and further purified, Obtain 2.4g solids.Yield 52%.1H NMR(500MHz,CDCl3) δ (ppm) 7.43 (ddd, J=8.8,2.4,0.6Hz, 1H), 7.21 (ddd, J=9.4,2.4,1.2Hz, 1H), 2.75 (s, 3H)13C NMR(126MHz,CDCl3)δ(ppm)164.84, 162.83,155.07,154.95,152.90,133.54,133.45,120.08,119.84,102.34,102.15,18.03.
The preparation of iodo- 7- methyl benzo [d] [1,2,5] thiadiazoles (compound 8) of the fluoro- 4- of 5-
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by fluoro- 4- methyl benzo [d] [1,2, the 5] thiadiazoles of 6- (3.0g, 17.8mmol) is dissolved in 100mL tetrahydrofurans, and lithium diisopropylamine (12mL, 2.0M in THF) is added dropwise, and 1h is stirred at -78 DEG C.Then the solution of iodine (9.0g, 35.6mmol are dissolved in 50mL THF) is added drop-wise in reaction mixture, Reaction unit is restored to room temperature, reaction stirring 8 hours.After reaction, reaction is quenched with water and pours into Na2SO3Aqueous solution In, and extracted with dichloromethane.Oil phase is dried with anhydrous magnesium sulfate, vacuum distillation removes solvent.Crude product passed through silica gel Column further purifies, and obtains 4.4g white solids.Yield 84%.1H NMR(500MHz,CDCl3)δ(ppm)7.25–7.21(m, 1H),2.72(s,3H).13C NMR(126MHz,CDCl3)δ(ppm)165.30,163.31,156.03,155.95,151.30, 133.64,133.56,119.87,119.62,67.46,67.22,17.70,17.68.
The preparation of the fluoro- 4- iodobenzenes of 7- (two bromomethyls) -5- simultaneously [c] [1,2,5] thiadiazoles (compound 9)
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by iodo- 7- methyl benzo [d] [1,2, the 5] thiophenes two of the fluoro- 4- of 5- Azoles (0.50g, 1.7mmol), N- bromo-succinimides (1.8g, 10.2mmol), benzoyl peroxide (0.21g, It 0.85mmol) is dissolved in 20mL carbon tetrachloride, reaction unit is then increased to 90 DEG C, react 8h.After reaction, it will react Device restores to room temperature, and reaction mixture is poured into water, and is extracted with dichloromethane, is washed with brine, and uses MgSO4It is dry. Crude product passed through silicagel column and further purified, and obtained 0.45g white solids.Yield 58%.1H NMR(500MHz,CDCl3)δ (ppm) 8.00 (d, J=9.2Hz, 1H), 7.40 (s, 1H)13C NMR(126MHz,CDCl3)δ(ppm)161.52,159.50, 153.61,153.56,147.00,134.24,134.17,121.34,121.09,100.34,100.14,32.62.
The preparation of the fluoro- 7- iodobenzenes of 6- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (compound 10)
Under argon gas atmosphere, in 100mL two-mouth bottles, by the fluoro- 4- iodobenzenes of 7- (two bromomethyls) -5- simultaneously [C] [1,2,5] thiophene two Azoles (1.0g, 2.2mmol) is dissolved in 15mL formic acid, and reaction unit is increased to 90 DEG C, reacts 6h.After reaction, it will react Device restores to room temperature, and after formic acid is removed, crude product passed through silicagel column and further purifies, and obtained 0.6g yellow solids.Production Rate 88%.1H NMR(500MHz,CDCl3) δ (ppm) 10.79 (d, J=2.3Hz, 1H), 8.08 (d, J=8.4Hz, 1H)13C NMR(126MHz,CDCl3)δ(ppm)187.27,187.26,161.53,159.50,154.78,154.74,149.78, 126.65,126.60,121.78,121.55,106.20,106.00.
7,7'- (two indeno [1,2-B of (4- hexyls the phenyl) -4,9- dihydro-s- of 4,4,9,9- tetra- benzos：5,6-B'] two thiophenes Two diyls of fen -2,7-) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (compound 11) preparation
Under argon gas atmosphere, the fluoro- 7- iodobenzenes of 6- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (310mg, 1.0mmol), 2,7- is bis- (tin trimethyl) -4,9- dihydros -4,4,9,9- four (4- hexyls phenyl)-s- indenos not [1,2-b：5,6-b'] Dithiophene (400mg, 0.4mmol) and Pd (PPh3)4(46mg, 0.04mmol) is added in two-mouth bottle, is dissolved in the toluene of 15mL, will Reaction unit increases temperature to 110 DEG C, reacts 48h.After reaction, when toluene move fall after, crude product passed through silicagel column into One step purifies, and obtains 365mg red solids.Yield：62%.1H NMR(500MHz,CDCl3) δ (ppm) 10.72 (d, J= 1.9Hz, 2H), 8.46 (s, 2H), 8.10 (d, J=12.0Hz, 2H), 7.63 (s, 2H), 7.26 (d, J=8.2Hz, 8H), 7.12 (d, J=8.2Hz, 8H), 2.61-2.54 (m, 8H), 1.59 (dd, J=15.2,7.5Hz, 8H), 1.36-1.25 (m, 24H), 0.87 (t, J=6.8Hz, 12H)13C NMR(126MHz,CDCl3)δ(ppm)187.37,158.91,157.22,156.87, 154.72,153.14,153.06,151.17,147.78,147.71,141.98,141.51,136.01,135.26,135.20, 128.97,128.88,128.67,128.03,123.88,123.81,122.85,122.61,119.60,119.49,118.66, 63.34,35.72,31.85,31.47,29.84,29.28,22.73,14.23.Mass(MALDI-TOF):m/z,calcd for C78H76F2N4O2S4:1266.48；found:1266.435.
(5Z, 5'Z) -5,5-'- (((4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2-B： 5,6b'] Dithiophene -2,7- diyls) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -7,4- diyls)) bis- (methyl connection pentadienes)) The preparation of bis- (3- ethyl -2- Thioxothiazolidin -4- ketone) (abbreviation IFBR-p)
Under argon atmosphere, by 7,7'- (4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2- B：5,6-B'] two diyls of Dithiophene -2,7-) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (160mg, 0.13mmol), 3- ethyls rhodanine (210mg, 1.3mmol) is added in two-mouth bottle, is dissolved in the chloroform of 20mL.It will reaction Device is warming up to 60 DEG C, reacts 2h.After reaction, after reaction dissolvent is removed, crude product passed through silicagel column and further carried It is pure, obtain 152mg red solids.Yield：75%.
Hydrogen nuclear magnetic resonance spectrogram, carbon spectrogram, fluorine spectrogram and the mass spectrogram of the conjugated molecular material IFBR-p of preparation is respectively such as Shown in Fig. 1, Fig. 2, Fig. 3 and Fig. 4, the position at the peak in Fig. 1~Fig. 3 and integration are former with hydrogen atom, carbon in IFBR-p structures respectively The resonance of son and fluorine atom meets, and the corresponding m/z values in the position at the peak in Fig. 4 are consistent with the molecular weight of IFBR-p, characterization ginseng Number is as follows：
1H NMR(500MHz,CDCl3) δ (ppm) 8.42 (s, 2H), 8.40 (s, 2H), 7.60 (s, 2H), 7.58 (d, J= 12.9Hz, 2H), 7.25 (d, J=5.2Hz, 8H), 7.11 (d, J=8.3Hz, 8H), 4.23 (q, J=7.1Hz, 4H), 2.60- 2.55 (m, 8H), 1.63-1.56 (m, 9H), 1.36-1.26 (m, 30H), 0.86 (t, J=6.8Hz, 12H)1H NMR (500MHz,CD2Cl2) δ (ppm) 8.44 (s, 2H), 8.38 (s, 2H), 7.65 (s, 2H), 7.61 (d, J=13.0Hz, 2H), 7.27 (d, J=8.3Hz, 8H), 7.13 (d, J=8.4Hz, 8H), 4.22 (q, J=7.2Hz, 4H), 2.62-2.53 (m, 8H), 1.63-1.54 (m, 8H), 1.36-1.25 (m, 30H), 0.86 (t, J=7.0Hz, 12H)13C NMR(126MHz,CD2Cl2)δ (ppm)193.25,167.87,157.55,155.10,152.93,152.84,152.27,146.95,146.88,142.61, 142.03,136.35,136.33,129.12,128.38,128.16,128.09,127.37,125.68,125.66,124.67, 124.59,122.43,122.16,118.88,63.79,40.59,36.06,32.28,32.03,30.26,29.69,23.17, 14.41,12.57.19F NMR(471MHz,CD2Cl2) δ (ppm) -107.29 (d, J=12.9Hz) .Mass (MALDI-TOF): m/z,calcd for C88H86F2N6O2S8:1552.45；found:1552.471.
Embodiment 3
Based on indacene 1,4-Dithiapentalene, 5- fluorobenzene, simultaneously [d] [1,2,5] thiadiazoles and rhodanine conjugated molecular material be (referred to as IFBR-d synthesis)
Synthetic route is as follows：
The preparation of the fluoro- 6- nitroanilines (compound 12) of the bromo- 4- of 2-
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of the 250mL equipped with condensing unit, by the fluoro- 2- nitroanilines of 4- (5g, It 32mmol) is dissolved in 35mL acetic acid, dropwise by liquid Br2(10.24g, 64mmol) is added in reaction unit.Then reaction is filled Storing is placed in oil bath pan, is warming up to 60 DEG C and is kept for 8 hours.After reaction, reaction mixture is then poured into NaHSO3 In aqueous solution, 7g yellow solids are obtained.Product is without further purifying.Yield 93%.
The preparation of the bromo- 5- fluorobenzene -1,2- diamines (compound 13) of 3-
Under argon gas atmosphere, in two mouthfuls of round-bottomed flasks of the 250mL equipped with reflux condenser, the fluoro- 6- nitre of the bromo- 4- of 2- is added in Base aniline (10g, 42.5mmol) simultaneously adds in 50ml ethyl alcohol and makes its dissolving, while add in Fe powder (12g, 212.6mmol), then Reaction unit is positioned in oil bath pan, is warming up to 80 DEG C.It is then slowly added into the diluted HCl of use 30mL ethyl alcohol (45mL). Reaction reflux 8 hours, and cool the temperature to room temperature.Reaction solution is poured into cold NaOH aqueous solutions, ethyl acetate extraction is anhydrous Magnesium sulfate is dried.Vacuum distillation removes solvent, obtains 7.9g brown oils.Obtained crude product is without further being carried It is pure, directly carry out next step reaction.
The preparation of the bromo- 6- fluorobenzene of 4- simultaneously [c] [1,2,5] thiadiazoles (compound 14)
Under argon gas atmosphere, in two mouthfuls of round-bottomed flasks of the 250mL equipped with reflux condenser, bromo- 5- fluorobenzene -1 of 3- is added in, 2- diamines (8.0g, 39.0mmol), and add in 80ml pyridines and make its dissolving.Reaction unit is positioned in ice bath (0 DEG C) to stir It mixes 30 minutes, thionyl chloride (13.9g, 117mmol) is added dropwise in reaction unit.Then round-bottomed flask is put into oil bath pan In temperature of speaking slowly rise to 60 DEG C, reaction is for 24 hours.After reaction, reaction mixture is poured into water, that dichloromethane extraction It takes.Oil phase is dried with anhydrous magnesium sulfate, vacuum distillation removes solvent.Crude product passed through silicagel column and further purified, and obtained 4.3g solid.Yield 38%.1H NMR(500MHz,CDCl3) δ (ppm) 7.73 (dd, J=8.4,2.3Hz, 1H), 7.61 (dd, J =8.4,2.3Hz, 1H)13C NMR(126MHz,CDCl3)δ(ppm)164.12,162.09,154.09,153.97,151.06, 124.29,124.03,115.28,115.18,104.63,104.44.
The preparation of fluoro- 4- methyl benzo [d] [1,2,5] thiadiazoles (compound 15) of the bromo- 5- of 7-
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by the bromo- 6- fluorobenzene of 4- simultaneously [c] [1,2,5] thiadiazoles (6.0g, 25.8mmol) is dissolved in 50mL tetrahydrofurans, and lithium diisopropylamine (12mL, 2.0M in THF) is added dropwise, and 1h is stirred at -78 DEG C.Then the solution of iodine (16.7mL, 2.0M in THF) is added drop-wise in reaction mixture, reaction is filled Recovery is put to room temperature, reaction stirring 8 hours dries oil phase with anhydrous magnesium sulfate, and vacuum distillation removes solvent.Crude product passes through It crosses silicagel column further to purify, obtains 0.63g white solids.Yield 10%.1H NMR(500MHz,CDCl3)δ(ppm)7.69 (t, J=8.4Hz, 1H), 2.58 (s, 3H)13C NMR(126MHz,CDCl3)δ(ppm)161.13,159.14,155.20, 155.10,150.72,124.18,123.92,114.77,114.61,111.36,111.26,10.27,10.25.
The preparation of the bromo- 4- of 7- (two bromomethyls) -5- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles (compound 16)
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by fluoro- 4- methyl benzo [d] [1,2, the 5] thiophenes two of the bromo- 5- of 7- Azoles (0.70g, 2.8mmol), N- bromo-succinimides (2.1g, 11.3mmol), benzoyl peroxide (0.34g, 1.4mmol) It is dissolved in 20mL carbon tetrachloride, reaction unit is then increased to 90 DEG C, react 8h.After reaction, reaction unit is restored To room temperature, reaction mixture is poured into water, and is extracted with dichloromethane, is washed with brine, uses MgSO4It is dry.Crude product passes through It crossed silicagel column further to purify, and obtained 0.45g white solids.Yield 61%.1H NMR(500MHz,CDCl3)δ(ppm)7.75 (d, J=9.8Hz, 1H), 7.32 (d, J=1.2Hz, 1H)13C NMR(126MHz,CDCl3)δ(ppm)151.12,150.51, 150.44,124.05,123.80,118.00,117.89,117.26,117.15,24.89,24.86.
The preparation of the bromo- 5- fluorobenzene of 7- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (compound 17)
Under argon gas atmosphere, in 100mL two-mouth bottles, by the fluoro- 4- iodobenzenes of 7- (two bromomethyls) -5- simultaneously [C] [1,2,5] thiophene two Azoles (0.65g, 1.6mmol) is dissolved in 15mL formic acid, and reaction unit is increased to 90 DEG C, reacts 6h.After reaction, it will react Device restores to room temperature, and after formic acid is removed, crude product passed through silicagel column and further purifies, and obtained 0.36g yellow solids.Production Rate 86%.1H NMR(500MHz,CDCl3) δ (ppm) 10.72 (d, J=0.6Hz, 1H), 7.87 (d, J=10.1Hz, 1H)13C NMR(126MHz,CDCl3)δ(ppm)184.78,184.74,167.09,164.92,151.56,150.91,150.84, 124.22,123.97,122.96,122.85,112.96,112.89.
7,7'- (two indeno [1,2-B of (4- hexyls the phenyl) -4,9- dihydro-s- of 4,4,9,9- tetra- benzos：5,6-B'] two thiophenes Fen -2,7- diyls) two (5- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (compounds 18) preparation
Under argon atmosphere, the bromo- 5- fluorobenzene of 7- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (180mg, 0.69mmol), 2,7- Bis- (tin trimethyl) -4,9- dihydros -4,4,9,9- four (4- hexyls phenyl)-s- indenos not [1,2-b：5,6-b'] Dithiophene (370mg, 0.30mmol) and tetra-triphenylphosphine palladium (35mg, 0.03mmol) are added in two-mouth bottle, are dissolved in the toluene of 15mL In, reaction unit is increased into temperature to 110 DEG C, reacts 48h.After reaction, after toluene moves, crude product passed through silica gel Column further purifies, and obtains 250mg red solids.Yield：66%.1H NMR(500MHz,CDCl3)δ(ppm)10.68(s, 2H), 8.20 (s, 2H), 7.69 (d, J=12.2Hz, 2H), 7.60 (s, 2H), 7.23 (d, J=8.3Hz, 8H), 7.12 (d, J= 8.4Hz, 8H), 2.61-2.55 (m, 8H), 1.64-1.55 (m, 8H), 1.36-1.24 (m, 24H), 0.86 (t, J=7.0Hz, 12H).13C NMR(126MHz,CDCl3)δ(ppm)184.66,184.62,168.54,166.41,157.86,154.76, 152.95,152.88,149.58,147.91,142.20,141.18,140.27,140.25,135.98,134.93,134.83, 128.76,127.96,126.88,118.67,113.92,113.68,111.31,111.24,63.38,35.71,31.85, 31.49,29.27,22.73,14.23.Mass(MALDI-TOF):m/z,calcd for C78H76F2N4O2S4:1266.48； found:1267.530.
(5Z, 5'Z) -5,5-'- (((4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2-B： 5,6b'] Dithiophene -2,7- diyls) bis- (5- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -7,4- diyls)) bis- (methyl connection pentadienes)) The preparation of bis- (3- ethyl -2- Thioxothiazolidin -4- ketone) (abbreviation IFBR-d)
Under argon atmosphere, by 7,7'- (4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- benzos, two indenos [1,2- B：5,6-B'] Dithiophene -2,7- diyl) two (5- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (180mg, 0.14mmol), 3- ethyls rhodanine (230mg, 1.42mmol) is added in two-mouth bottle, is dissolved in the chloroform of 20mL.Reaction unit is heated up To 60 DEG C, 2h is reacted.After reaction, after reaction dissolvent is removed, crude product passed through silicagel column and further purified, and obtained 120mg red solids.Yield：55%.1H NMR(500MHz,CDCl3)δ(ppm)8.23(s,2H),8.13(s,2H),7.69 (d, J=12.1Hz, 2H), 7.58 (s, 2H), 7.23 (d, J=8.3Hz, 8H), 7.12 (d, J=8.4Hz, 8H), 4.22 (q, J =7.2Hz, 4H), 2.63-2.53 (m, 8H), 1.64-1.55 (m, 8H), 1.37-1.25 (m, 30H), 0.87 (dd, J=9.3, 4.5Hz,13H).13C NMR(126MHz,CDCl3)δ(ppm)194.99,194.97,167.92,163.76,161.69, 157.75,154.59,153.24,153.17,149.38,146.77,142.10,141.32,140.61,140.59,135.92, 131.23,131.14,128.72,127.98,127.52,127.50,125.87,121.88,121.85,118.47,114.47, 114.22,110.35,110.23,63.34,40.04,35.72,31.85,31.49,29.28,22.73,14.23,12.46.19F NMR(471MHz,CDCl3) δ (ppm) -104.89 (d, J=12.1Hz) .Mass (MALDI-TOF):m/z,calcd for C88H86F2N6O2S8:1552.45；found:1552.597.
The nuclear magnetic resonance spectroscopy comparison diagram of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 As shown in figure 5, the specific distribution of the hydrogen atom in conjugated backbone can be told as shown in Figure 5, in figure, with fluorine atom far from place It is compared in the IFBR-d of the electron unit of molecular center, fluorine atom is close to the H3 and H4 of the IFBR-p of center electron unit The position at peak is moved toward low field, shows the position difference of strong electrophilic fluorine atom and the chemical environment of neighbouring hydrogen atom is caused to occur Variation.
Embodiment 4
Based on indacene 1,4-Dithiapentalene, 5- fluorobenzene, simultaneously [d] [1,2,3] thiadiazoles and rhodanine conjugated molecular material be (referred to as IFBR-p-d synthesis)
Synthetic route is as follows：
The fluoro- 7- of 5- ((4- hexyls the phenyl) -4,9- dihydro-s- of 4,4,9,9- tetra- indacene [1,2-b:5,6-b'] Dithiophene- 2- yls) benzo [c] [1,2,5] thiadiazoles -4- formaldehyde (compound 19) preparation
Under argon atmospher, by (4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- indacene [1,2-b:5,6-b'] two Thiophene -2- bases) tin trimethyl (150mg, 0.14mmol), the bromo- 5- fluorobenzene of 7- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (91mg, It 0.35mmol) is added in two-mouth bottle, is dissolved in the toluene of 15mL with tetra-triphenylphosphine palladium (35mg, 0.03mmol), it will be anti- Device is answered to increase temperature to 110 DEG C, after reacting 48 hours, stops heating, and cool the temperature to room temperature.Post processing：By reaction solution It is poured into water, ethyl acetate extraction, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.After vacuum distillation, crude product silicon Rubber column gel column purifies, and leacheate is dichloromethane and petroleum ether mixed solvent, finally obtains 100mg red solids.(yield：66%) matter Spectrum：Calculated value：1086.50；Measured value：1085.87. elemental analysis：Calculated value:C, 78.41%；H, 6.95%；N, 2.58%； S, 8.84%. measured value:C, 77.98%；H, 6.88%；N, 2.62%；S, 9.03%.
(4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydros-s- draws the fluoro- 7- of 4- (1,3- dioxolan 2 yls) -5- Up to province [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiadiazoles (compound 20) preparation
Under argon atmospher, by the fluoro- 7- of 5- (4,4,9,9- tetra- (4- hexyls phenyl) -4,9- dihydro-s- indacene [1,2-b:5, 6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiadiazoles -4- formaldehyde (271mg, 0.25mmol), ethylene glycol (78mg, It 1.25mmol) is added in two-mouth bottle, is dissolved in the toluene of 15mL with a small amount of acetic acid, reaction unit is increased into temperature to 110 DEG C, after reacting 48 hours, stop heating, and cool the temperature to room temperature.Post processing：Reaction solution is poured into water, ethyl acetate extraction It takes, saturated sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.After vacuum distillation, the purification of crude product purified by silica gel column, leacheate two Chloromethanes and petroleum ether mixed solvent, finally obtain 238mg red solids.(yield：84%) mass spectrum：Calculated value：1130.53； Measured value：1130.72. elemental analysis：Calculated value:C, 77.48%；H, 7.04%；N, 2.48%；S, 8.50%. measured value:C, 77.6%；H, 7.12%；N, 2.62%；S, 8.22%.
The fluoro- 7- of 4- (1,3- dioxolan 2 yls) -5- (4,4,9,9- tetra- (4- hexyls phenyl) -7- (tin trimethyl) - 4,9- dihydro-s- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiadiazoles (compound 21) system It is standby
Under argon gas atmosphere, in two mouthfuls of round-bottomed bottles of 100mL, by the fluoro- 7- of 4- (1,3- dioxolan 2 yl) -5- (4, (4- hexyls the phenyl) -4,9- dihydro-s- of 4,9,9- tetra- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2, 5] thiadiazoles (453mg, 0.4mmol) is dissolved in 50mL tetrahydrofurans, and lithium diisopropylamine (0.3mL, 2.0M tetrahydrochysene is added dropwise Tetrahydrofuran solution), and stirred 1 hour at -78 DEG C.Then by trimethyltin chloride (0.45mL, 2.0M, tetrahydrofuran solution) Solution is added drop-wise in reaction mixture, reaction unit is restored to room temperature, reaction is stirred overnight.After reaction, reaction is used Water quenching is gone out and is poured into water, and is extracted with dichloromethane.Oil phase is dried with anhydrous magnesium sulfate, vacuum distillation removes solvent.Slightly Product passed through silicagel column and further purified, and obtained 0.45g red solids.(yield：86%) mass spectrum：Calculated value：1294.49； Measured value：1294.77. elemental analysis：Calculated value:C, 70.52%；H, 6.77%；N, 2.16%；S, 7.43%. measured value:C, 70.60%；H, 6.80%；N, 2.04%；S, 7.22%.
7- (7- (7- (1,3- dioxolan 2 yls) -6- fluorobenzene [c] [1,2,5] thiadiazoles -4- bases) -4,4,9,9- four (4- hexyls phenyl) -7- (tin trimethyl) -4,9- dihydro-s- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) -6- fluorobenzene The preparation of [c] [1,2,5] thiadiazoles -4- formaldehyde (compound 22)
Under argon atmospher, by the fluoro- 7- of 4- (1,3- dioxolan 2 yl) -5- (4,4,9,9- tetra- (4- hexyls phenyl) -7- (tin trimethyl) -4,9- dihydro-s- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiadiazoles (150mg, 0.12mmol), the fluoro- 7- iodobenzenes of 6- simultaneously [c] [1,2,5] thiadiazoles -4- formic acid (54mg, 0.17mmol) and four triphens Base phosphine palladium (35mg, 0.03mmol) is added in two-mouth bottle, is dissolved in the toluene of 15mL, by reaction unit raising temperature extremely 110 DEG C, after reacting 48 hours, stop heating, and cool the temperature to room temperature.Post processing：Reaction solution is poured into water, ethyl acetate Extraction, saturated sodium-chloride water solution are washed, anhydrous magnesium sulfate drying.After vacuum distillation, crude product purified by silica gel column purifies, and leacheate is Dichloromethane and petroleum ether mixed solvent, finally obtain 85mg red solids.(yield：54%) mass spectrum：Calculated value：1310.51； Measured value：1310.77. elemental analysis：Calculated value:C, 73.25%；H, 6.15%；N, 4.27%；S, 9.78%. measured value:C, 73.66%；H, 6.44%；N, 4.26%；S, 9.72%.
The fluoro- 7- of 5- (7- (fluoro- 7- formyls benzo [c] [1,2,5] thiadiazoles -4- bases of 5-) (4- hexyl benzenes of -4,4,9,9- four Base) -7- (tin trimethyl) -4,9- dihydro-s- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiophene The preparation of diazole -4- formaldehyde (compound 23)
Under argon atmospher, by 7- (7- (7- (1,3- dioxolan 2 yl) -6- fluorobenzene [c] [1,2,5] thiadiazoles -4- Base) (4- hexyls phenyl) -7- (the tin trimethyl) -4,9- dihydro-s- of -4,4,9,9- four indacene [1,2-b:5,6-b'] two thiophenes Fen -2- bases) -6- fluorobenzene [c] [1,2,5] thiadiazoles -4- formaldehyde (85mg, 65mmol) is dissolved in the tetrahydrofuran of 15mL, adds Enter a small amount of hydrochloric acid, stop stirring after being stirred at room temperature 48 hours.Post processing：Reaction solution is poured into water, ethyl acetate extraction, saturation Sodium-chloride water solution is washed, anhydrous magnesium sulfate drying.After vacuum distillation, the purification of crude product purified by silica gel column, leacheate is dichloromethane With petroleum ether mixed solvent, 77mg red solids are finally obtained.(yield：94%) mass spectrum：Calculated value：1266.48；Measured value： 1266.52. elemental analysis：Calculated value:C, 73.90%；H, 6.04%；N, 4.42%；S, 10.12%. measured value:C, 73.96%；H, 6.44%；N, 4.62%；S, 10.08%.
(Z) -3- ethyls -5- ((7- (7- (7- ((Z)-(3- ethyl -4- oxygen -2- thioxothiazole -5- subunits) methyl) -5- fluorine Benzo [c] [1,2,5] thiadiazoles -4- bases) (4- hexyls phenyl) -7- (the tin trimethyl) -4,9- dihydros of -4,4,9,9- four-s- draws Up to province [1,2-b:5,6-b'] Dithiophene -2- bases) -5- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- bases) methyl) the thio thiophenes of -2- The preparation of azoles -4- ketone (abbreviation IFBR-p-d)
Under argon atmosphere, by the fluoro- 7- of 5- (7- (fluoro- 7- formyls benzo [c] [1,2, the 5] thiadiazoles -4- bases of 5-) -4,4,9, (4- hexyls phenyl) -7- (the tin trimethyl) -4,9- dihydro-s- of 9- tetra- indacene [1,2-b:5,6-b'] Dithiophene -2- bases) benzo [c] [1,2,5] thiadiazoles -4- formaldehyde (70mg, 0.06mmol), 3- ethyls rhodanine (97mg, 0.6mmol) are added to two-mouth bottle In, it is dissolved in the chloroform of 20mL.Reaction unit is warming up to 60 DEG C, reacts 2h.After reaction, reaction dissolvent is removed Afterwards, crude product passed through silicagel column and further purified, and obtained 70mg red solids.(yield：75%) mass spectrum：Calculated value： 1552.45；Measured value：1552.77 elemental analysis：Calculated value:C, 68.01%；H, 5.58%；N, 5.41%；S, 16.50%. Measured value:C, 69.02%；H, 5.66%；N, 5.40%；S, 16.69%.
Embodiment 5
Based on dithieno benzene thiophene, 5- fluorobenzene simultaneously [d] [1,2,5] thiadiazoles and rhodanine conjugated molecular material The synthesis of (abbreviation DT-FBR-p)
Synthetic route is as follows：
7,7'- (5,10- bis- (2- (2- ethylhexyls) -3- hexyl thiophene -5- bases)-benzo [1,2-b:4,5-b '] two thiophenes Fen simultaneously [3,2-b] thiophene -2,7- diyls) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (compound 25) preparation
Under argon atmosphere, the iodo- 5- fluorobenzene of 7- simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde (133mg, 0.43mmol), 2,7- Two (trimethyl-tin-radical) -5,10- two (2- (2- ethylhexyls) -3- hexyl thiophene -5- bases)-benzo [1,2-b:4,5-b '] two thiophenes Simultaneously [3,2-b] thiophene (200mg, 0.17mmol) and tetra-triphenylphosphine palladium (35mg, 0.03mmol) are added in two-mouth bottle for fen, molten Solution increases temperature to 110 DEG C in the toluene of 15mL, by reaction unit, reacts 48h.After reaction, after toluene moves, slightly Product passed through silicagel column and further purified, and obtained 170mg red solids.(yield：82%).Mass spectrum：Calculated value： 1218.31；Measured value：1218.55.Elemental analysis：Calculated value:C, 63.02%；H, 5.62%；N, 4.59%；S, 21.03%. Measured value:C, 63.12%；H, 5.66%；N, 4.57%；S, 20.96%.
(5Z, 5'Z) -5,5'- (((5,10- bis- (2- (2- ethylhexyls) -3- hexyl thiophene -5- bases)-benzos [1,2-b: 4,5-b '] dithieno [3,2-b] thiophene -2,7- diyls) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -7,4- diyls)) double (methyl connection pentadiene)) bis- (3- ethyl -2- Thioxothiazolidin -4- ketone) (abbreviation DT-FBR-p) preparation
Under argon atmosphere, by 7,7'- (5,10- bis- (2- (2- ethylhexyls) -3- hexyl thiophene -5- bases)-benzos [1,2- b:4,5-b '] dithieno [3,2-b] thiophene -2,7- diyls) bis- (6- fluorobenzene simultaneously [c] [1,2,5] thiadiazoles -4- formaldehyde) (160mg, 0.13mmol), 3- ethyls rhodanine (210mg, 1.3mmol) are added in two-mouth bottle, are dissolved in the chloroform of 20mL In.Reaction unit is warming up to 60 DEG C, is reacted 2 hours.After reaction, after reaction dissolvent is removed, crude product passed through silicon Rubber column gel column further purifies, and obtains 151mg red solids.(yield：77%) mass spectrum：Calculated value：1504.28；Measured value： 1503.30.Elemental analysis：Calculated value:C, 59.01%；H, 5.22%；N, 5.58%；S, 25.54%. measured value:C, 59.22%；H, 5.44%；N, 5.57%；S, 125.60%.
The fundamental property test of small molecule is obtained based on embodiment 2 and 3
(1) thermogravimetric analysis (TGA) is Netzsch TG 209 using instrument, and heating rate is 20 DEG C/min, and atmosphere is nitrogen Gas.
Thermogravimetric curve comparison diagram such as Fig. 6 of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 It is shown, it will be appreciated from fig. 6 that the thermogravimetric curve of IFBR-p and IFBR-d shows that the temperature of two kinds of molecule weightlessness 5% is all higher than 300 DEG C.
The differential scanning calorimetric curve pair of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 Than scheming as shown in fig. 7, as shown in Figure 7, the differential calorimetry curve of IFBR-p and IFBR-d show two kinds of molecules in 30-300 Without there is apparent heat deflection phenomenon at DEG C.
(2) ultraviolet-visible light (UV-vis) absorption spectrum is Shimadzu UV-3600UV-vis-NIR spectrometers.
The cycle of the electro-chemical test of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 lies prostrate Pacify curve comparison figure as shown in figure 8, as shown in Figure 8, the absorption curve of IFBR-p and IFBR-d show the ABSORPTION EDGE of two kinds of molecules Band is all higher than 700nm, while IFBR-p is nearlyer 25nm than the absorption red shift of IFBR-d.
(3) cyclic voltammetry (CV) test uses CHI630E electrochemical workstations.Saturated calomel electrode, platinum electrode and Glass-carbon electrode difference reference electrode, auxiliary electrode and working electrode.Tetrabutyl ammonium hexafluorophosphate (Bu4NPF6) acetonitrile solvent (0.1mol L-1).Sweep speed is set as 100mV s-1.Molecular orbital energy level can pass through formula：EHOMO=-[4.8+e (Eox–EFc/Fc+)](eV)；ELUMO=-[4.8+e (Ere–EFc/Fc+)](eV)。
Absorption spectrum comparison diagram such as Fig. 9 of conjugated molecular material IFBR-p and IFBR-d that embodiment 2 is prepared with embodiment 3 It is shown, as shown in Figure 9, the Cyclic voltamogram curve of IFBR-p and IFBR-d can be evaluated whether its HOMO/LUMO energy level be respectively- 5.64/ -3.73eV and -5.67/ -3.74eV.
The preparation of polymer solar cells based on 2 and 3 gained small molecule of embodiment
First, by the poly- 3,4-ethylene dioxythiophene polystyrene doped sulfonate (trade name of 40nm thickness：Germany congratulates Li Shi AI 4083) layer is spin-coated on through 4 minutes ozone-plasmas treated indium tin oxide transparent conductive semiconductor glass (ITO) lining On bottom, then ITO substrates are placed on 150 DEG C of warm table and are annealed 15 minutes, are then passed to the gloves controlled to water oxygen automatic control In case；
It is 1 by mass ratio:1.5 polymeric donor (4,8- bis- (5- (2- ethylhexyls) thiophene -2- bases) benzene [1,2-b: 4,5-b'] Dithiophene and 2- octyl groups -6- (octyl group) -4,8- two (thiophene -2-yl)-[1,2,3] triazole [4,5-f] iso-indoles -5,7 (2H, 6H)-diketone alternate copolymer, code name PTzBI) with the blend of prepared conjugation small molecule it is dissolved in chlorobenzene In, and it is spun on PEDOT:As photoactive layer on PSS, photoactive layer thickness is 385nm；After spin coating, by substrate as The heat treatment of 10 minutes is carried out on 100 DEG C of warm table to active layer；PEDOT:PSS and active layer thickness utilize Tencor 500 surface profilers of Alpha-step measure；
After annealing, (3 '-((N, N- the dimethyl)-N- second ammoniums)-the third of 9,9- bis- of one layer of 5nm of spin coating on active layer Base) -2,7- fluorenes) (0.5 milligram every milliliter of methanol is molten with the alternate copolymer dibromo (PFN-Br) of 2,7- (9,9- octyl groups fluorenes) Liquid)；Finally, ITO substrates are placed on mask plate, and in (1.0 × 10 in vacuum evaporation storehouse-6Mbar one) is deposited on active layer For the aluminium that layer thickness is 100nm as cathode, the effective area for also defining device is 0.16cm2；Utilize STM-100/MF Sycon quartz crystal monitorings evaporation rate and thickness；
(the 100mW cm under AM1.5 solar spectrums-2), the volt-ampere that examination device is measured using 2400 power supplys of Keithley is special Linearity curve (J-V)；Solar simulation lamp model SAN-EI, XES-40S1；The test equipment model of external quantum efficiency (EQE) Solar Cell Spectral Response Measurement System QE-R3011(Enlitech Co.,Ltd.)； The corresponding light intensity of each wavelength is calibrated using standard monocrystalline silicon solar cell.
The solar cell volt-ampere of conjugated molecular material IFBR-p and IFBR-d prepared based on embodiment 2 and embodiment 3 is special Linearity curve comparison diagram is as shown in Figure 10, as shown in Figure 10, is blended respectively with IFBR-p and IFBR-d using donor polymer PTzBI Polymer solar cells are prepared as photoactive layer, its electricity conversion is obtained by the device VA characteristic curve in the figure Respectively 7.44% and 5.28%.

Claims (10)

1. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle, which is characterized in that chemical structural formula is as follows：
In formula, Ar1 and Ar2 are electron unit, and Ar3 is electrophilic unit；X1、X2、X3And X4H or F is independently chosen from, and X1、X2、X3And X4It is asynchronously H；
Electron unit Ar1 is any one of following structural formula：
Electron unit Ar2 is any one of following structural formula：
Wherein, R is hydrogen, C1-C30 alkyl or is more than one carbon atom by oxygen atom, alkenyl, alkynyl, aryl, hydroxyl, ammonia Base, carbonyl, carboxyl, nitro, phenyl or the C1-C30 alkyl of thienyl substitution are taken for more than one hydrogen atom by halogen atom The C1-C30 alkyl in generation；
Electrophilic unit Ar3 is any one of following chemical structural formula：
In formula, symbol " * " represents structure and the doubly linked positions of molecule C=C.
2. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 1, which is characterized in that For a fluorine substituent；In formula, X1For F, X2、X3And X4It is H；Or X2For F, X1、X3And X4It is H.
3. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 1, which is characterized in that For two fluorine substituents；In formula, X1And X2It is F, X3And X4It is H；Or X1And X3It is F, X2And X4It is H；Or X1And X4It is F, X2And X3It is H；Or X2And X3It is F, X1And X4It is H.
4. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 1, which is characterized in that For three fluorine substituents；In formula, X1、X2And X3Equal F, X4For H；Or X1、X2And X4It is F, X3For H.
5. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 1, which is characterized in that For four fluorine substituents；In formula, X1、X2、X3And X4Equal F.
6. prepare a kind of side of the conjugated molecular material based on fluorine atom substitution benzheterocycle of claim 1-5 any one of them Method, which is characterized in that include the following steps：
(1) X will be contained1、X2With Ar2 to halogenated benzheterocycle -4- formaldehyde, containing X3、X4With Ar2 to halogenated benzheterocycle -4- formaldehyde And the Ar1 containing double alkyl tin groups is dissolved in organic solvent, by Stille coupling reactions, synthesis both sides end group is aldehyde radical Acceptor-donor-receptor type intermediate product；
(2) acceptor-donor-receptor type intermediate product of the both sides end group for aldehyde radical is dissolved in Ar3 unit molecules in organic solvent, It is reacted by Knoevenagel, obtains the conjugated molecular material based on fluorine atom substitution benzheterocycle.
7. a kind of preparation method of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 6, It is characterized in that, in step (1), containing X1、X2With Ar2 to halogenated benzheterocycle -4- formaldehyde and containing X3、X4With Ar2 to halogeno-benzene And the mole ratio of the integral molar quantity of heterocycle -4- formaldehyde and the Ar1 containing double alkyl tin groups are 2.5~3：1；Containing X1、X2And Ar2 To halogenated benzheterocycle -4- formaldehyde and containing X3、X4It is 1 to the molar ratio of halogenated benzheterocycle -4- formaldehyde with Ar2：1；It is described Stille coupling reactions carry out under atmosphere of inert gases；The organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, chlorine Imitative or tetrahydrofuran；The temperature of the Stille coupling reactions is 80-110 DEG C, and the reaction time is 24-48 hours.
8. a kind of preparation method of conjugated molecular material based on fluorine atom substitution benzheterocycle according to claim 6, It is characterized in that, in step (2), the both sides end group is acceptor-donor-receptor type intermediate product of aldehyde radical and Ar3 units point The molar ratio of son is 1:10, and add in the alkali molecules that molar equivalent is 10%；The alkali molecules include pyridine, piperidines or three Ethamine；The organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro-benzenes, chloroform or tetrahydrofuran；The Knoevenagel is anti- It should be carried out under atmosphere of inert gases；The temperature of the Knoevenagel reactions is 50-60 DEG C, reaction time 50- 120min。
9. a kind of conjugated molecular material based on fluorine atom substitution benzheterocycle of claim 1-5 any one of them has in preparation Application in the active layer of machine photoelectric device, which is characterized in that the conjugated molecular material of benzheterocycle will be replaced based on fluorine atom It is dissolved in being formed in organic solvent with Donor compound and be dissolved in, the activity of organic electro-optic device is made up of solution processing method Layer.
10. application according to claim 9, which is characterized in that the conjugation point based on fluorine atom substitution benzheterocycle The mass ratio of sub- material and Donor compound is 0~1.5:1；The organic solvent includes toluene, dimethylbenzene, chlorobenzene, dichloro One or more of benzene, chloroform, tetrahydrofuran and methyltetrahydrofuran；The thickness of the active layer is 5nm~3 μm.
CN201710994403.6A 2017-10-23 2017-10-23 A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application Pending CN108218887A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710994403.6A CN108218887A (en) 2017-10-23 2017-10-23 A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710994403.6A CN108218887A (en) 2017-10-23 2017-10-23 A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application

Publications (1)

Publication Number Publication Date
CN108218887A true CN108218887A (en) 2018-06-29

Family

ID=62654910

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710994403.6A Pending CN108218887A (en) 2017-10-23 2017-10-23 A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application

Country Status (1)

Country Link
CN (1) CN108218887A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369571A (en) * 2018-12-04 2019-02-22 无锡市赛乐新材料科技有限公司 One kind containing the bromo- 4- aldehyde radical diazosulfide of fluorine-substituted 7- and its synthetic method
CN110746372A (en) * 2019-11-28 2020-02-04 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 Small molecule acceptor material with low lowest unoccupied molecular orbital energy level, preparation method and application
CN112608333A (en) * 2020-12-29 2021-04-06 华南理工大学 Micromolecules based on dithiadiazole carbazole derivatives, synthetic method thereof and application of micromolecules in organic photoelectric devices
CN113248451A (en) * 2020-04-27 2021-08-13 广东聚华印刷显示技术有限公司 Quinoxaline compound, polymer, organic electronic device and display panel
WO2022033993A1 (en) 2020-08-11 2022-02-17 Cambridge Display Technology Limited Photoactive material
CN114560871A (en) * 2021-04-19 2022-05-31 中国科学院大学 Synthesis method of selective substituted functionalized dithienyl imide luminescent material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
WENKAI ZHONG, 等: "Enhanced Photovoltaic Performance of Ternary Polymer Solar Cells by Incorporation of a Narrow-Bandgap Nonfullerene Acceptor", 《CHEMISTRY OF MATERIALS》 *
WENKAI ZHONG, 等: "Regioisomeric Non-Fullerene Acceptors Containing Fluorobenzo[c][1,2,5]thiadiazole Unit for Polymer Solar Cells", 《ACS APPLIED MATERIALS & INTERFACES》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109369571A (en) * 2018-12-04 2019-02-22 无锡市赛乐新材料科技有限公司 One kind containing the bromo- 4- aldehyde radical diazosulfide of fluorine-substituted 7- and its synthetic method
CN110746372A (en) * 2019-11-28 2020-02-04 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 Small molecule acceptor material with low lowest unoccupied molecular orbital energy level, preparation method and application
CN113248451A (en) * 2020-04-27 2021-08-13 广东聚华印刷显示技术有限公司 Quinoxaline compound, polymer, organic electronic device and display panel
CN113248451B (en) * 2020-04-27 2023-04-28 广东聚华印刷显示技术有限公司 Quinoxaline compound, polymer, organic electronic device and display panel
WO2022033993A1 (en) 2020-08-11 2022-02-17 Cambridge Display Technology Limited Photoactive material
CN112608333A (en) * 2020-12-29 2021-04-06 华南理工大学 Micromolecules based on dithiadiazole carbazole derivatives, synthetic method thereof and application of micromolecules in organic photoelectric devices
CN114560871A (en) * 2021-04-19 2022-05-31 中国科学院大学 Synthesis method of selective substituted functionalized dithienyl imide luminescent material

Similar Documents

Publication Publication Date Title
CN108218887A (en) A kind of conjugated molecular material based on fluorine atom substitution benzheterocycle and preparation method and application
CN107011361A (en) Organic photoelectric acceptor material and its preparation method and application
Fan et al. Efficient polymer solar cells based on a new quinoxaline derivative with fluorinated phenyl side chain
Li et al. An expanded isoindigo unit as a new building block for a conjugated polymer leading to high-performance solar cells
CN107074830A (en) The D A polymer based on difluoro bithiophene for photovoltaic applications
CN110128633B (en) Preparation method and application of low-HOMO energy level polymer donor material
CN104004165B (en) Electron donor polymer and application thereof containing S, S-dioxo-dibenzothiophene unit
CN104086752A (en) Benzodithiophene polymer, its preparation method, semiconductor composition containing it, and solar cell using it
CN107057044A (en) Heteroatom-substituted benzothiadiazole-based polymer donor material and preparation method and application thereof
CN105753851B (en) Tetrafluoride Benzoquinoxalines compound and tetrafluoride Benzoquinoxalines based polyalcohol and its preparation method and application
Qiu et al. Effect of fluorine substitution on photovoltaic properties of alkoxyphenyl substituted benzo [1, 2-b: 4, 5-b′] dithiophene-based small molecules
Huang et al. Donor–acceptor conjugated polymers based on thieno [3, 2-b] indole (TI) and 2, 1, 3-benzothiadiazole (BT) for high efficiency polymer solar cells
Akhtar et al. A symmetric benzoselenadiazole based D–A–D small molecule for solution processed bulk-heterojunction organic solar cells
KR102291239B1 (en) N-type organic semiconducting compounds, manufacturing method thereof, and organic photovoltaics containing the same
Zhang et al. A new wide bandgap small molecular acceptor based on indenofluorene derivatives for fullerene-free organic solar cells
Wen et al. Synthesis and photovoltaic properties of low‐bandgap 4, 7‐dithien‐2‐yl‐2, 1, 3‐benzothiadiazole‐based poly (heteroarylenevinylene) s
Qiu et al. An asymmetric small molecule based on thieno [2, 3-f] benzofuran for efficient organic solar cells
Tong et al. Large branched alkylthienyl bridged naphtho [1, 2-c: 5, 6-c′] bis [1, 2, 5] thiadiazole-containing low bandgap copolymers: Synthesis and photovoltaic application
CN108409944A (en) A kind of conjugated polymer and its preparation method and application replacing conjugation side chain containing chlorine
Ma et al. Small molecules based on tetrazine unit for efficient performance solution-processed organic solar cells
Peng et al. Development of s-tetrazine-based polymers for efficient polymer solar cells by controlling appropriate molecular aggregation
Kim et al. Synthesis and characterization of indeno [1, 2-b] fluorene-based low bandgap copolymers for photovoltaic cells
Agneeswari et al. Effects of the incorporation of an additional pyrrolo [3, 4-c] pyrrole-1, 3-dione unit on the repeating unit of highly efficient large band gap polymers containing benzodithiophene and pyrrolo [3, 4-c] pyrrole-1, 3-dione derivatives
Zhu et al. Triisopropylsilylethynyl substituted benzodithiophene copolymers: synthesis, properties and photovoltaic characterization
He et al. Two new fluorinated copolymers based on thieno [2, 3-f] benzofuran for efficient polymer solar cells

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180629

WD01 Invention patent application deemed withdrawn after publication