CN108794509A - One kind is using thiazole and thiazole is the A of core2-π-A1-π-A2The preparation and application of type small molecule receptor material - Google Patents

One kind is using thiazole and thiazole is the A of core2-π-A1-π-A2The preparation and application of type small molecule receptor material Download PDF

Info

Publication number
CN108794509A
CN108794509A CN201810519723.0A CN201810519723A CN108794509A CN 108794509 A CN108794509 A CN 108794509A CN 201810519723 A CN201810519723 A CN 201810519723A CN 108794509 A CN108794509 A CN 108794509A
Authority
CN
China
Prior art keywords
thiazole
small molecule
molecule receptor
receptor material
type small
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.)
Granted
Application number
CN201810519723.0A
Other languages
Chinese (zh)
Other versions
CN108794509B (en
Inventor
朱卫国
彭文红
张斌
朱梦冰
顾子倩
马超
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.)
Changzhou University
Original Assignee
Changzhou University
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 Changzhou University filed Critical Changzhou University
Priority to CN201810519723.0A priority Critical patent/CN108794509B/en
Publication of CN108794509A publication Critical patent/CN108794509A/en
Application granted granted Critical
Publication of CN108794509B publication Critical patent/CN108794509B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains two hetero rings
    • C07D513/04—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
    • 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
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • 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
    • H10K85/656—Aromatic compounds comprising a hetero atom comprising two or more different heteroatoms per ring
    • H10K85/6565—Oxadiazole compounds
    • 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
    • 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

Abstract

The present invention relates to one kind using thiazole and thiazole weak electron acceptor groups is the A of core2‑π‑A1‑π‑A2Application of the preparation and such material of type small molecule receptor material as the electron acceptor material in photoactive layer in organic photovoltaic battery field.Such small molecule receptor material contains only mono-/bis-aromatic rings, has the characteristics that simple in structure, synthesis step is few and has excellent performance.Body heterojunction organic photovoltaic cell is made by Solution processing techniques using this kind of small molecule receptor material and polymer donor material, the ceiling capacity transformation efficiency of battery device is up to 8.77%.The present invention realizes A2‑π‑A1‑π‑A2Efficient energy conversion of the type small molecule receptor material in organic polymer solar cell has powerful application prospect.

Description

One kind is using thiazole and thiazole is the A of core2-π-A1-π-A2Type small molecule receptor material It prepares and applies
Technical field
The present invention relates to organic photovoltaic fields, and in particular to one kind is with simple in structure, thiazole and thiazole weak electron receptor Unit is the A of core2-π-A1-π-A2The preparation of type small molecule receptor material and such material are as the electronics in photoactive layer Application of the receptor in organic photovoltaic battery field.
Background technology
With the high speed development of current world economy, the energy and environmental crisis are increasingly sharpened, need of the people to clean energy resource Ask also more and more urgent.As inexhaustible, nexhaustible green energy resource, how to carry out efficiently utilizing to it becomes solar energy The research hotspot of scientists.Solar energy can be efficiently converted into electric energy by organic photovoltaic cell (OSCs), have of low cost, matter The features such as measuring light, translucent, flexible so that it is demonstrated by huge in fields such as wearable device, portable energy sources Application potential.
Active layer material is to determine the key factor of organic photovoltaic cell performance, it is mainly by donor material and acceptor material Composition.By the research of decades, donor material and fullerene electron acceptor material are rapidly developed, and are largely had excellent performance Small molecule, polymer donor material and some fullerene derivative receptor materials be developed, as DRCN5T, PBDB-T, PTB7-Th and J51[1]Deng；Emerging non-fullerene acceptor material is also developed rapidly in recent years, is formd small molecule and is gathered Close the non-fullerene acceptor material of object two major classes.Currently, the energy conversion efficiency (PCE) of non-fullerene polymer solar cell is Higher than 13%[2-4], it has been more than the device performance levels based on fullerene acceptor.
In terms of small molecule receptor material, condensed ring class A-D-A types that Zhan Xiaowei team of Peking University in 2015 reports for the first time Small molecule receptor ITIC is the acceptor material that research in recent years is most extensive, device efficiency is most excellent.This kind of ITIC derivatives receptor material Material all illustrates wide application prospect in single layer binary, ternary and laminated device[5-8].Currently, the condensed ring of acceptor material System is by condensed ring skeleton, side chain and electronics end group is drawn to form.Its main feature is that：(1) condensed ring core is mainly the big planar conjugate of rigidity Structure, strong π-π interactions are conducive to intermolecular accumulation, improve carrier mobility；(2) condensed ring core has strongly Electron donation can occur Intramolecular electron transfer effect between electronics end group with drawing, assign molecule wide and strong visible or even close Infrared absorption.This kind of acceptor material by modifying condensed ring, side chain and end-group structure, can easily interaction between regulatory molecule, Energy level and absorption.They are combined with the polymer donor material of middle width strip gap prepares OSCs, and the photoelectric conversion efficiency of device is continuous It breaks through.For example, Liao Liang lifes in 2016 et al. are reported based on ten and condensed ring electron acceptor material IDTIDSe-IC, it is total with J51 Mixed device obtains 8.02% PCE values[9]；The nine of the exploitations such as Xiao Wei and condensed ring electron acceptor material INIC3 are accounted within 2017, Its molar extinction coefficient is up to 2.1 × 105M-1cm-1, the device being blended with polymer donor material FTAZ obtains 11.5% PCE values[10]；The same year, the eight and condensed ring electron acceptor material IOIC2 that they report again, the device being blended with FTAZ obtain 12.3% PCE values[11].Recently, the team also report another eight and condensed ring electron acceptor material film absorption 600 The PSCs devices PCE prepared is blended with PTB7-Th and reaches 12% by~950nm[12].Seven the most classical and condensed ring acceptor material It is ITIC, ITIC and PBDTS-TDZ collocation are prepared device by 2018 professors Nian Pengqiang, and the PCE values of device are up to 12.80%.When When using concatenated device configurations, the PCE of device is further increased to 13.35%, this is organic photovoltaic cell of connecting at that time Peak[4]；The same year Yang Chuluo etc. is reported based on benzo two (cyclopentadiene 1,4-Dithiapentalene) acceptor material BDTThIT-M, with PBDB-T, which is blended, obtains the device that PCE is 12.12%[14].It accounts within 2017 Xiao Wei groups and reports six and condensed ring based on naphthalene nucleus Acceptor material IHIC1, and with the device that is blended of polymer donor material FTAZ, the efficiency of device is 9.21%[15]；The same year, Alex K-Y.Jen et al. develop the another kind of six and condensed ring acceptor material 4TIC based on bithiophene, and the absorption of material film exists 600~900nm is based on than seven and condensed ring acceptor material (ITIC) and nine simultaneously condensed ring acceptor material (INIC) red shift about 110nm PTB7-Th:The PCE that single layer device is blended in 4TIC is the 10.43%, PCE of laminated device up to 12.62%[16].Account for Xiao Wei within 2018 Team reports five based on indacene 1,4-Dithiapentalene (IDT) and condensed ring acceptor material IDIC1, they are by it and polymeric donor Material FTAZ is blended, and it is 7.13% device to obtain PCE[17]；The same year, Bao Zhishan et al. introduce the oxygen atom of electron In IDT units, synthesis obtained five yuan of condensed ring acceptor material Ph-DTDP-IC of another structure novel, they by it with PBDB-T is blended, and obtains the device that PCE is 7.73%[18].Zhu Xiao chapters in 2017 et al. develop indenoindene be core four simultaneously Condensed ring acceptor material NITI, such material are demonstrated by the low band gaps of 1.49eV, and molar absorption coefficient in the solution is up to 1.90 ×105m-1cm-1, the PCE of device is 12.74%[19].2017 Nian Pengqiang seminars reduce the conjugation of intermediate electron nuclear unit Structure devises main chain using fluorenes as the ternary condensed ring acceptor material SFBRCN of core, and the molecular optics greater band gap is poly- with narrow band gap The PCE for closing the OSCs devices that preparation is blended in object donor PTB7-Th has reached 10.26%[20]。
It summarizes and finds：In the acceptor material of these reports, intermediate condensed cyclic structure is substantially the above condensed cyclic structure of ternary, The few document report of the acceptor material of binary and following condensed cyclic structure.The synthesis of acceptor material based on big condensed ring division center at This height, film forming stability can adjust difficulty.For this purpose, we select intermediate condensed ring, for simple in structure, thiazole, simultaneously thiazole binary is thick Ring weak electron receptor unit builds A2-π-A1-π-A2Type small molecule receptor material.Thiazole in molecule and thiazole, can enhance Intermolecular π-π and dipole effect, optimize crystal property, the chemical property of molecule, improve photoactive layer pattern and therefore open It is sending out simple in structure, based on the A that thiazole and thiazole are core2-π-A1-π-A2Type small molecule receptor material, for China's innovation and development Efficiently, inexpensive organic photovoltaic acceptor material is of great significance.
It is attached：Leading reference
[1]S.X.Li,W.Q.Liu,C.-Z.Li,M.M.Shi,H.Z.Chen,small,2017,1701120.
[2]W.C.Zhao,S.S.Li,H.F.Yao,S.Q.Zhang,Y.Zhang,B.Yang,J.H.Hou, J.Am.Chem.Soc.,2017,139(21):7148-715.
[3]Y.Cui,H.F.Yao,B.W.Gao,Y.P.Qin,S.Q.Zhang,B.Yang,C.He,B.W.Xu, J.H.Hou,J.Am.Chem.Soc.,2017,139(21):7302-7309.
[4]X.P.Xu,T.Yu,Z.Z.Bi,W.Ma,Y.Li,Q.Peng,Adv.Mater.,2017,1703973.
[5]Y.Cui,H.F.Yao,C.Y.Yang,S.Q.Zhang,J.H.Hou,ActaPolym.Sin.,2017,1, 135-142.
[6]Z.Xiao,X.Jia,L.M.Ding,Sci.Bull.,2017,62,1562-1564.
[7]W.N.Li,L.Ye,S.S.Li,H.F.Yao,H.Ade,J.H.Hou,Adv.Mater.,2018,1707170.
[8]J.Sun,X.L.Ma,Z.H.Zhang,J.S.Yu,J.Zhou,X.X.Yin,L.Q.Yang,R.Y.Geng, R.H.Zhu,F.J.Zhang,W.H.Tang,Adv.Mater.,2018,1707150.
[9]Y.X.Li,D.P.Qian,L.Zhong,J.D.Lin,Z.Q.Jiang,Z.G.Zhang,Z.J.Zhang, Y.F.Li,L.S.Liao,F.L.Zhang,Nano Energy,2016,27,430-438.
[10]S.X.Dai,F.W.Zhao,Q.Q.Zhang,T.-K.Lau,T.F.Li,K.Liu,Q.D.Ling, C.R.Wang,X.H.Lu,W.You,X.W.Zhan,J.Am.Chem.Soc.,2017,139,1336-1343.
[11]J.S.Zhu,Z.F.Ke,Q.Q.Zhang,J.Y.Wang,S.X.Dai,Y.Wu,Y.Xu,Y.Z.Lin,W.Ma, W.You,X.W.Zhan,Adv.Mater.,2017,1704713.
[12]T.F.Li,S.X.Dai,Z.F.Ke,L.X.Yang,J.Y.Wang,C.Q.Yan,W.Ma,X.W.Zhan, Adv.Mater.,2018,1705969.
[13]Q.F.Cao,W.T.Xiong,H.J.Chen,G.S.Cai,G.Wang,L.P.Zheng,Y.M.Sun, J.Mater.Chem.A,2017,5,7451.
[14]Q.S.An,W.Gao,F.J.Zhang,J.Wang,M.Zhang,K.L.Wu,X.L.Ma,Z.H.Hu, C.Q.Jiao,C.L.Yang,J.Mater.Chem.A,2018,DOI:10.1039/c7ta10763c.
[15]J.S.Zhu,Y.Wu,J.Rech,J.Y.Wang,K.Liu,T.F.Li,Y.Z.Lin,W.Ma,W.You, X.W.Zhan,J.Mater.Chem.C,2018,6(1):66-71.
[16]X.L.Shi,L.J.Zuo,S.B.Jo,K.Gao,F.Lin,F.Liu,Al.K-Y.Jen,Chem.Mater., 2017,29(19):8369-8376.
[17]J.S.Zhu,Y.Wu,J.Rech,J.Y.Wang,K.Liu,T.F.Li,Y.Z.Lin,W.Ma,W.You, X.W.Zhan,J.Mater.Chem.C,2018,6,66-71.
[18]L.S.Yang,M.Li,J.S.Song,Y.Y.Zhou,Z.S.Bo,H.Wang,Adv.Funct.Mater., 2018,1705927.
[19]S.J.Xu,Z.C.Zhou,W.Y.Liu,Z.B.Zhang,F.Liu,H.P.Yan,X.Z.Zhu, Adv.Mater.,2017,1704510.
[20]G.J.Zhang,G.F.Yang,H.Yan,J.-H.Kim,H.Ade,W.L.Wu,X.P.Xu,Y.W.Duan, Q.Peng,Adv.Mater.,2017,1606054.
Invention content
The present invention is intended to provide it is a kind of completely new, the more simple small molecule receptor material of structure is constructed and preparation method. It selects monocycle or simultaneously cyclic group constructs A2-π-A1-π-A2Type small molecule receptor material, intercalated nucleus A1Selecting has weak drawing electro The thiazole and thiazole of energy pass through end group receptor A of the π bridge units connection with strong electron-withdrawing ability of electron2.Intramolecular/ Between the effect of D-A electric charge transfers and thiazole and thiazole dipole effect, wide and strong visible or even near-infrared may be implemented and inhale It receives, improves the π-π and dipolar interaction of molecule, improve the efficiency of light absorption of material, the highest for reducing material captures molecule rail Road (HOMO) energy level.By Solution processing techniques, this kind of small molecule receptor material and polymer donor material are blended, made non- Fullerene organic photovoltaic cell (OSCs) is, it can be achieved that efficient energy conversion of such small molecule material in OSCs.
It is provided by the invention using thiazole and thiazole as the A of core2-π-A1-π-A2Type small molecule receptor material has following general formula Structure：
A1For following thiazole and thiazole weak electron acceptor groups：
π (D) is following medium electron donor mono-/bis-aromatic ring group：
Wherein R1、R2For following group：(1) hydrogen atom；(2) carbon atom number is C1~C20Straight chain or alkyl containing branch, Alkoxy or alkylthio group；(3) monocyclic aryls such as thiophene, benzene containing the substitution of alkyl, alkoxy or alkylthio group.
X is the hetero atoms such as O, S, Se, Te.
A2Electron group is haled to be following：
Wherein：Y1、Y2For hydrogen atom, fluorine atom or chlorine atom.
Using thiazole and thiazole is the A of core2-π-A1-π-A2The preparation method of type small molecule receptor material is：
R will be carried1、R2Substituted five-ring heterocycles π endo compounds and quantitative N- bromo-succinimides (molar ratio 1: 1.1) single bromine product of No. 2 positions substitution is obtained through bromination reaction；At -78 DEG C, by this product successively and reagent n-butyllithium and N, Dinethylformamide acts on, and synthesis obtains single aldehyde product of No. 2 positions substitution；At 200 DEG C, by single aldehyde product and rubeanic acid (molar ratio 1:0.5), appropriate phenol is added in reaction bulb, and after reacting 4-8 hour, π-A are obtained through column chromatography for separation1- π chemical combination Object.Then, at -78 DEG C, by π-A1- π compounds are successively acted on reagent n-butyllithium and n,N-Dimethylformamide, synthesis Obtain π-A1The dialdehyde monomer of-π is acted on reagent n-butyllithium and trimethyltin chloride, and synthesis obtains π-A1Double tin chemical combination of-π Object；Under the catalytic action of tetrakis triphenylphosphine palladium, π-A1Double tin compounds of-π and bromo Y1、Y2Substituted diazosulfide Single aldehyde monomer effect, must contain diazosulfide derivative combination π-A through Stille coupling reactions1The dialdehyde monomer of-π；By this list Body or π-A1The dialdehyde compound of-π is passed through with above-mentioned end group condensation reaction to get to a series of A2-π-A1-π-A2Type small molecule by Body material.
Small molecule receptor material provided by the invention contains only mono-/bis-aromatic group, and the model of constructing of molecule is A2-π-A1- π-A2.Compared with the small molecule receptor material currently reported, this kind of small molecule receptor material has the characteristics that：(1) molecule In thiazole and thiazole, have rigidity planar structure, can enhance intermolecular π-π and dipole effect, optimize the knot of molecule Brilliant performance, chemical property improve photoactive layer pattern, put forward high molecular carrier mobility；(2) nitrogen in thiazole and thiazole Atom has certain electrophilic characteristic, can effectively drop low molecular HOMO and lumo energy；(3) select alkyl, alkoxy or Five unit monocycle electron heterocyclic aryls of the modifications such as alkylthio group are π bridges, the property such as dissolubility, absorption and flatness of adjustable molecular Energy；(4) end group is selected than centronucleus A1The stronger unit of electron-withdrawing ability is conducive to the dissociation and transmission of exciton, further excellent Change and absorbs and the performances such as carrier mobility；(5) mono-/bis-ring aryl unit simple in structure is selected to construct small molecule receptor material The advantages such as material has synthesis step few, and manufacturing cost is low, therefore, developing this kind of small molecule receptor material has powerful application Potentiality.
The application of the present invention is：Using the organic molecule designed and developed as photoactive layer acceptor material, purchased with business The polymer donor material bought is blended under different proportion, makes body heterojunction organic photovoltaic cell device, realizes device Efficient photoelectricity treater is converted.
The organic photovoltaic cell device includes indium tin oxide target (ITO) electro-conductive glass anode, cathodic modification layer, photolytic activity Layer, anode modification layer, cathode.Active layer material is that small molecule receptor material of the present invention is given with commercially available polymer Body material.
Description of the drawings
Fig. 1 is the uv-visible absorption spectra of TTz1 of the present invention and TTz2
Fig. 2 is the cyclic voltammetry curve of TTz1 of the present invention and TTz2
Fig. 3 is TTz1 of the present invention:J71 and TTz2:The J-V curves of J71 organic photovoltaic cell devices
Fig. 4 is TTz1 of the present invention:J71 and TTz2:The EQE curves of J71 organic photovoltaic cell devices
Specific implementation mode
Below by specific embodiment, the invention will be further described, but these specific embodiments are not in any way It limits the scope of the invention.
Embodiment 1
Using thiazole and thiazole is the A of core2-π-A1-π-A2The synthesis of type small molecule receptor material TTz1.
The synthetic route of TTz1 is as follows:
The synthesis of the bromo- 3- of 1.1 2- (2- butyl octyls) thiophene (2)
In 250mL there-necked flasks, compound 1 (10g, 39.6mmol) is sequentially added, N- bromo-succinimides (8.46g, 47.6mmol), 150mL glacial acetic acid.It being protected from light under protection, reacts at room temperature 12h, stop reaction, reaction solution is transferred in separatory funnel, Be added 50mL distilled water, extracted through dichloromethane, anhydrous magnesium sulfate drying after, vacuum distillation removal organic solvent, residue with Petroleum ether is that eluant, eluent carries out column chromatography for separation, obtains colorless oil compound 2 (12.2g, yield 93%).1H NMR (400MHz,CDCl3) δ 7.18 (d, J=5.6Hz, 1H), 6.76 (d, J=5.6Hz, 1H), 2.49 (d, J=7.2Hz, 2H), 1.65 (dd, J=11.1,5.9Hz, 1H), 1.29-1.24 (m, 16H), 0.88 (t, J=6.8Hz, 6H).
The synthesis of 1.2 3- (2- butyl octyls) thiophene -2-formaldehydes (3)
In 250mL two-mouth bottles, compound 2 (12g, 36.2mmol) and anhydrous tetrahydro furan (120mL) is added.Nitrogen is protected It protects, n-BuLi (2.5M, 18.8mL, 47.1mmol) is slowly added dropwise at -78 DEG C, after being stirred to react 1h, is added at one time DMF (10.6g, 12mL) after the reaction was continued 1h, warms naturally to room temperature, overnight.Reaction solution is poured into water, dichloromethane extraction, Merge organic phase and is dried with anhydrous magnesium sulfate.Vacuum distillation removal organic solvent, residue is with petroleum ether：Dichloromethane (1: 1,v:V) it is eluant, eluent, carries out column chromatography for separation, obtain yellow oily compound 3 (8.5g, yield 84%).1H NMR (400MHz,CDCl3) δ 10.03 (s, 1H), 7.64 (d, J=4.2Hz, 1H), 6.98 (d, J=4.2Hz, 1H), 2.88 (d, J= 7.2Hz, 2H), 1.69-1.65 (m, 1H), 1.27-1.24 (m, 16H), 0.87 (t, J=6.7Hz, 6H).
The synthesis of 1.3 2,5- bis- (3- (2- butyl octyls) thiophene -2- bases) thiazoles simultaneously [5,4-d] thiazole (4)
In 100mL single port bottles, compound 3 (8.0g, 28.5mmol) is sequentially added, dithiooxamide (1.71g, 14.3mmol) and phenol (25mL), under nitrogen protection, 200 DEG C of back flow reaction 8h.It is cooled to room temperature, crude product is with petroleum ether:Two Chloromethanes (4:1,v:V) it is eluant, eluent, carries out column chromatography for separation, obtain the sticky compound 4 (2.9g, yield 32%) of brown color.1H NMR(300MHz,CDCl3) δ 7.34 (d, J=5.1Hz, 1H), 6.95 (d, J=5.1Hz, 1H), 2.92 (d, J=7.3Hz, 2H), 1.81 (s, 1H), 1.30-1.23 (m, 16H), 0.86 (t, J=6.5Hz, 6H).
1.4 2,5- bis- (3- (2- butyl octyls) -5- (tributylestannyl) thiophene -2- bases) thiazoles simultaneously [5,4-d] thiophene The synthesis of azoles (5)
In 100mL two-mouth bottles, compound 4 (2.5g, 3.9mmol) and anhydrous tetrahydro furan (40mL) is added, nitrogen is protected It protects, n-BuLi (2.5M, 5.5mL, 13.7mmol) is slowly added dropwise at -78 DEG C, is stirred to react 2h, is added at one time trimethyl chlorine Change tin (1.0M, 13.7mL, 13.7mL), after the reaction was continued 1h, warms naturally to room temperature, overnight.Reaction solution is poured into water, two Chloromethanes extracts, and merges organic phase and is dried with anhydrous magnesium sulfate.Vacuum distillation removal organic solvent, residue precipitating is in methanol In, filter to obtain yellow solid compound 5 (3.2g, yield 85%).1H NMR(400MHz,CDCl3)δ7.00(s,1H),2.94 (d, J=7.3Hz, 2H), 1.88-1.76 (m, 1H), 1.33-1.25 (m, 16H), 0.95-0.82 (m, 6H), 0.51-0.33 (m, 9H)。
Bis- (4- (2- butyl octyls) thiophene -5,2- of 1.5 7,7'- (5,5'- (thiazole simultaneously [5,4-d] thiazole -2,5- diyls) Diyl)) synthesis of two (benzo [c] [1,2,5] thiadiazoles -4- formaldehyde) (7)
In bis- mouthfuls of bottles of 50mL, compound 5 (1.28g, 1.32mmol) is sequentially added, tetrakis triphenylphosphine palladium (76mg, 5%) back flow reaction is for 24 hours and compound 6 (0.64g, 2.64mmol) and toluene (30mL), under nitrogen protection, at 110 DEG C.Stop Reaction, is cooled to room temperature, reaction solution is poured into water, and dichloromethane extraction merges organic phase and dried with anhydrous magnesium sulfate.Subtract Pressure distillation removal organic solvent, residue is with petroleum ether:Dichloromethane (1:2,v:V) it is eluant, eluent, carries out column chromatography for separation, obtain Violet solid compound 7 (0.78g, yield 61%).1H NMR(300MHz,CDCl3) δ 10.70 (s, 1H), 8.21 (d, J= 7.5Hz, 1H), 8.14 (s, 1H), 8.01 (d, J=7.5Hz, 1H), 3.00 (d, J=7.3Hz, 2H), 2.01-1.87 (m, 1H), 1.50-1.16(m,16H),0.94-0.84(m,6H)。
The synthesis of 1.6 TTz1
In bis- mouthfuls of bottles of 100mL, compound 7 (300mg, 0.31mmol) is sequentially added, malononitrile (205mg, 3.10mmol), alkali alumina (400mg) and dry toluene (50mL), nitrogen protection are stirred to react 12h at 85 DEG C.It is cooled to Room temperature pours into precipitating in 200mL absolute methanols, filters, crude product is with petroleum ether:Chloroform (1:2,v:V) it is eluant, eluent, into Row column chromatography for separation obtains maroon solid chemical compound TTz1 (220mg, production with metallic luster through chloroform and acetone recrystallization 67%) rate is.1H NMR(300MHz,CDCl3) δ 8.73 (d, J=2.7Hz, 2H), 8.14 (s, 1H), 8.01 (dd, J=8.0, 2.4Hz, 1H), 2.98 (d, J=6.8Hz, 2H), 2.01-1.83 (m, 1H), 1.51-1.17 (m, 16H), 0.94-0.84 (m, 6H)。
Embodiment 2
Using thiazole and thiazole is the A of core2-π-A1-π-A2The synthesis of type small molecule receptor material TTz2.
The synthetic route of TTz2 is as follows:
In bis- mouthfuls of bottles of 100mL, compound 7 (200mg, 0.21mmol) is sequentially added, compound 8 (382mg, 2.07mmol), triethylamine (0.5mL) and chloroform (60mL), under nitrogen protection, 65 DEG C of back flow reactions are for 24 hours.It is cooled to room Temperature pours into precipitating in 200mL absolute methanols, filters, and crude product carries out column chromatography for separation, through three using chloroform as eluant, eluent Chloromethanes and acetone recrystallization obtain the maroon solid chemical compound TTz2 (230mg, yield 83%) with metallic luster.1H NMR (400MHz,CDCl3) δ 8.32 (s, 1H), 7.95 (s, 1H), 7.76 (d, J=7.7Hz, 1H), 7.56 (d, J=7.7Hz, 1H), 4.35-4.29 (m, 2H), 2.94-2.82 (m, 2H), 1.89 (t, J=16.9Hz, 1H), 1.51-1.26 (m, 19H), 0.97- 0.87(m,6H)。
Embodiment 3
The preparation and test of the performance characterization and photovoltaic device of small molecule receptor material TTz1 and TTz2：
Synthesized compound1H NMR spectras by Bruker Dex-300 NMR or 400NMR Instrument measurings, it is ultraviolet- Visible absorption spectra is measured by Shimadzu UV-800 ultraviolet-visible spectrophotometers, and cyclic voltammetry curve is using CHI630E electrifications Credit analyzer is tested.
Organic photovoltaic cell device based on the type small molecule receptor material includes indium tin oxide target (ITO) electro-conductive glass sun Pole, cathodic modification layer, photoactive layer, anode modification layer, cathode.Active layer material is small molecule receptor material of the present invention With commercially available polymer donor material, it is 1 that weight ratio, which is blended,:2.
The Photophysics of 3.1 organic molecule receptor TTz1 and TTz2 measure
Fig. 1 is ultraviolet-ray visible absorbing light of the organic molecule receptor TTz1 and TTz2 under chloroformic solution and filminess Spectrum, as seen from the figure, they all have wide and strong absorption in solution and film, and two are showed within the scope of 350-800nm Apparent characteristic absorption peak, short-wave band absorb the transition for belonging to molecular backbone π-π *, and long-wave band absorption peak belongs to intramolecular The electric charge transfer (ICT) of donor monomer to receptor unit acts on.Apparent red shift has occurred relative to the absorption of solution in film, and There is vibration acromion, this is the reason that packing of molecules enhances under solid state.By calculating, the optical band gap of TTz1 and TTz2 Respectively 1.65eV and 1.61eV (formula Eg=1240/ λ, wherein EgFor optical band gap, λ is film absorption maximum sideband value).
The chemical property of 3.2 organic molecule receptor TTz1 and TTz2 measures
The cyclic voltammetry curve of organic molecule receptor TTz1 and TTz2 in solid film is as shown in Fig. 2, public according to calculating Formula EHOMO=-(Eox+ 4.80) eV show that their HOMO energy levels are respectively -5.70eV and -5.50eV.According to calculation formula ELUMO=-(Ered+ 4.80) eV show that their lumo energy is respectively -3.86eV and -3.80eV.Thus calculate TTz1 and The electrochemistry band gap of TTz2 is respectively 1.84eV and 1.70eV.
The photovoltaic performance of 3.3 organic molecule acceptor material TTz1 and TTz2 measures
Active layer donor material using commercially available J71 as organic solar batteries, is synthesized with embodiment respectively Obtained TTz1 and TTz2 is active layer acceptor material, using the trans- device architecture ITO/ZnO/J71 of body heterojunction:TTz1 or J71:TTz2(1:2w/w；CF, 0.25%DIO, 3000r.p.m)/MoO3/ Ag constructs organic photovoltaic cell device.It is simulating too Sunlight light source (light intensity 100mW/cm2) under irradiation, the J-V curves of organic photovoltaic cell are measured as shown in figure 3, test result For：Based on J71:The organic photovoltaic cell shorted devices electric current J of TTz1scFor 15.43mA/cm2, open-circuit voltage VocFor 0.90V, fill out It is 63.18% to fill factor FF, and the energy conversion efficiency PCE for thus calculating battery is 8.77%；Based on J71:TTz2's is organic Solar cell shorted devices electric current JscFor 12.75mA/cm2, open-circuit voltage VocIt is 53.73% for 0.92V, fill factor FF, by This energy conversion efficiency PCE for calculating battery is 6.30%.
In optimal conditions (1:2w/w；CF, 0.25%DIO, 3000r.p.m), the J71 of test:TTz1 and J71:TTz2 EQE curves as shown in figure 4, the figure shows that the EQE test scopes of active layer corresponding to two small molecule receptors are 300- 800nm, wherein J71:The external quantum efficiency of TTz1 has been above 50% in 420-715nm ranges, is maximum at the places 576nm or so EQE values, up to 70%；And J71:The external quantum efficiency of TTz1 is more than 50% in 480-670nm ranges, is occurred at the places 587nm or so Maximum EQE values, up to 62%.
Despite the incorporation of preferred embodiment, the present invention is described, but the invention is not limited in above-described embodiment, It should be understood that appended claims summarise the scope of the present invention.Under the guidance of present inventive concept, those skilled in the art It should be recognized that certain change that various embodiments of the present invention scheme is carried out, it all will be by claims of the present invention Spirit and scope covered.

Claims (3)

1. one kind is using thiazole and thiazole is the A of core2-π-A1-π-A2Type small molecule receptor material has following general formula structure：
A1For following weak electron acceptor groups：
π (D) is following medium electron donor group：
Wherein R1、R2For following group：(1) hydrogen atom；(2) carbon atom number is C1~C20Straight chain or alkyl, alcoxyl containing branch Base or alkylthio group；(3) monocyclic aryls such as thiophene, benzene containing the substitution of alkyl, alkoxy or alkylthio group；
X is the hetero atoms such as O, S, Se, Te；
A2For following strong electron accepting groups：
Wherein：Y1、Y2For hydrogen atom, fluorine atom or chlorine atom.
2. A as described in claim 12-π-A1-π-A2Type small molecule receptor material, it is characterised in that in following molecular structure One kind (1-11).
3. according to the application of small molecule receptor material described in claim 1-2, it is characterised in that as photoactive layer acceptor material, It is blended with commercially available polymer donor material and makes that organic photovoltaic cell is formal or trans- device, be 1 to receptor blending ratio: 2。
CN201810519723.0A 2018-05-28 2018-05-28 A taking thiazolothiazole as core2-π-A1-π-A2Preparation and application of small molecule receptor material Active CN108794509B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810519723.0A CN108794509B (en) 2018-05-28 2018-05-28 A taking thiazolothiazole as core2-π-A1-π-A2Preparation and application of small molecule receptor material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810519723.0A CN108794509B (en) 2018-05-28 2018-05-28 A taking thiazolothiazole as core2-π-A1-π-A2Preparation and application of small molecule receptor material

Publications (2)

Publication Number Publication Date
CN108794509A true CN108794509A (en) 2018-11-13
CN108794509B CN108794509B (en) 2020-07-07

Family

ID=64090446

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810519723.0A Active CN108794509B (en) 2018-05-28 2018-05-28 A taking thiazolothiazole as core2-π-A1-π-A2Preparation and application of small molecule receptor material

Country Status (1)

Country Link
CN (1) CN108794509B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110379926A (en) * 2019-07-24 2019-10-25 浙江大学 A kind of organic photovoltaic cell based on benzo dithiazole class near-infrared receptor
CN110498793A (en) * 2019-08-12 2019-11-26 常州大学 Small molecule photovoltaic body phase material and its application based on rhodanine
CN110504365A (en) * 2019-08-29 2019-11-26 山东师范大学 A kind of photoactive layer, ternary organic solar batteries including the photoactive layer and its preparation method and application
CN111499624A (en) * 2020-04-21 2020-08-07 西南大学 Oligothiophene photovoltaic material and preparation method and application thereof
CN114057774A (en) * 2021-12-06 2022-02-18 电子科技大学 Organic photoelectric molecular material containing thienothiadiazole structure and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2233488A1 (en) * 2008-12-02 2010-09-29 Fuji Xerox Co., Ltd. Thiazolothiazole derivatives and organic electronic device using the same
WO2011051292A1 (en) * 2009-10-28 2011-05-05 University Of Washington Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells
CN104177374A (en) * 2013-05-27 2014-12-03 海洋王照明科技股份有限公司 Organic semiconductor material containing thiazolothiazole unit and preparation method thereof, and solar cell device

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2233488A1 (en) * 2008-12-02 2010-09-29 Fuji Xerox Co., Ltd. Thiazolothiazole derivatives and organic electronic device using the same
WO2011051292A1 (en) * 2009-10-28 2011-05-05 University Of Washington Copolymer semiconductors comprising thiazolothiazole or benzobisthiazole, or benzobisoxazole electron acceptor subunits, and electron donor subunits, and their uses in transistors and solar cells
CN104177374A (en) * 2013-05-27 2014-12-03 海洋王照明科技股份有限公司 Organic semiconductor material containing thiazolothiazole unit and preparation method thereof, and solar cell device

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110379926A (en) * 2019-07-24 2019-10-25 浙江大学 A kind of organic photovoltaic cell based on benzo dithiazole class near-infrared receptor
CN110379926B (en) * 2019-07-24 2021-07-06 浙江大学 Organic solar cell based on benzodithiazole near-infrared receptor
CN110498793A (en) * 2019-08-12 2019-11-26 常州大学 Small molecule photovoltaic body phase material and its application based on rhodanine
CN110498793B (en) * 2019-08-12 2022-12-16 常州大学 Small-molecule photovoltaic bulk phase material based on rhodanine and application thereof
CN110504365A (en) * 2019-08-29 2019-11-26 山东师范大学 A kind of photoactive layer, ternary organic solar batteries including the photoactive layer and its preparation method and application
CN111499624A (en) * 2020-04-21 2020-08-07 西南大学 Oligothiophene photovoltaic material and preparation method and application thereof
CN114057774A (en) * 2021-12-06 2022-02-18 电子科技大学 Organic photoelectric molecular material containing thienothiadiazole structure and preparation method and application thereof

Also Published As

Publication number Publication date
CN108794509B (en) 2020-07-07

Similar Documents

Publication Publication Date Title
CN108794509A (en) One kind is using thiazole and thiazole is the A of core2-π-A1-π-A2The preparation and application of type small molecule receptor material
Peng et al. Simple-structured small molecule acceptors constructed by a weakly electron-deficient thiazolothiazole core for high-efficiency non-fullerene organic solar cells
Deng et al. Triphenylamine-containing linear DAD molecules with benzothiadiazole as acceptor unit for bulk-heterojunction organic solar cells
Lu et al. Triindole-cored star-shaped molecules for organic solar cells
CN104718195A (en) Electronic devices using organic small molecule semiconducting compounds
CN108586496A (en) Zigzag type middle width strip gap small molecule electron donor materials based on the different chromene of thieno and its application
Li et al. Design and synthesis of star-burst triphenyamine-based π-conjugated molecules
CN105315273A (en) Polyceptor-structure small molecule compound and preparing method and application thereof
CN103554139B (en) Thiophene condensed 2,1,3-benzoxadiazole derivative and polymer thereof
CN106674491B (en) D-A type Polymer photovoltaic materials and its application based on the different chromene asymmetry electron unit of thieno
CN110003234A (en) One kind is based on the miscellaneous condensed ring D (A-Ar) of dithieno benzisoxa virtue2Type conjugated compound and its application
CN110054761A (en) One kind is based on oxygen/sulfur alkylation bithiophene donor element D-A type conjugated polymer and its preparation method and application
CN101787020A (en) Organic conjugated molecule capable of being processed by solution and application thereof in solar cells
CN110028654A (en) Based on naphthalimide-selenophen derivative organic n-type semi-conductor polymer material and the preparation method and application thereof
CN109970768A (en) Based on ten unitary condensed ring plane kernel D (A-Ar) of carbazole2Type organic photoelectric compound and preparation method and application
CN106977531A (en) A kind of two dimension conjugation furans organic micromolecule photovoltaic material of benzo two and its preparation method and application
CN104211926A (en) Donor material used for polymer solar battery, and polymerization monomer thereof
CN109081825A (en) A based on hexichol thio phenyl sulfone2(π-A1)2Non- fullerene acceptor material of type broad-band gap and its preparation method and application
CN109912621B (en) Asymmetric naphthalene nucleus small molecule receptor material and preparation method and application thereof
CN113527641B (en) Polymer material based on ester side chain substituted quinoxaline derivative and application thereof
CN111039961A (en) Preparation and application of oligomer photovoltaic donor material based on 5, 6-difluo benzothiadiazole unit
CN101962380B (en) Novel organic conjugated molecule and application thereof in organic solar cell
CN106700039B (en) Fluorinated pyridine [3,4-b] pyrazine compound and fluorinated pyridine [3,4-b] pyrazinyl copolymer material and application
WO2013016187A1 (en) Compounds for organic thin-film solar cells and organic thin-film solar cells
CN108440574B (en) Thiazole-containing organic small molecule and preparation method and application thereof

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
GR01 Patent grant
GR01 Patent grant