CN105315298A - A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules - Google Patents

A-D-A conjugated molecules based on hepta-condensed ring units and preparation method for A-D-A conjugated molecules and application of A-D-A conjugated molecules Download PDF

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CN105315298A
CN105315298A CN201410380113.9A CN201410380113A CN105315298A CN 105315298 A CN105315298 A CN 105315298A CN 201410380113 A CN201410380113 A CN 201410380113A CN 105315298 A CN105315298 A CN 105315298A
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condensed ring
ring unit
alkyl
conjugated molecule
preparation
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CN105315298B (en
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占肖卫
林禹泽
白会涛
王嘉宇
张明煜
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Institute of Chemistry CAS
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Abstract

The invention relates to A-D-A conjugated molecules by taking hepta-condensed ring units as cores and oligomerized five-membered aromatic rings as bridging units, wherein the tail ends are electron withdrawing units, a preparation method for the A-D-A conjugated molecules and an application of the molecules as active layer electron donors or electron acceptor materials in organic solar batteries (OPV). The A-D-A conjugated molecules based on hepta-condensed ring units can be processed by a solution method, have a proper energy level and have a relatively good sunlight capturing ability and heat stability, so that the molecules are an ideal material for the electron donors or electron acceptors in the organic solar batteries. The molecules have the structure as shown in the formula.

Description

Based on seven and A-D-A conjugated molecule and its preparation method and application of condensed ring unit
Technical field
The present invention relates to a class based on seven and condensed ring unit be core, oligomerisation 5-membered aromatic heterocycle is bridging unit, end is A-D-A conjugated molecule drawing electronic unit and preparation method thereof, and the application in organic solar batteries (OPV) as active coating electron donor(ED) or electron acceptor material of this quasi-molecule.
Background technology
Organic solar batteries has that cost is low, lightweight, flexible, solution processable the and big area advantage such as can to prepare, and is therefore paid close attention to widely in academia.In recent years, polymkeric substance and the development of small molecules solar cell rapidly, and achieve significant achievement (X.Zhan, D.Zhu, Conjugatedpolymersforhigh-efficiencyorganicphotovoltaics, Polym.Chem., 2010, Isosorbide-5-Nitrae 09; Y.Chen, X.Wan, G.Long, Highperformancephotovoltaicapplicationsusingsolution-pro cessedsmallmolecules, Acc.Chem.Res., 2013,46,2645; Y.-J.Cheng, S.-H.Yang, C.-S.Hsu, Synthesisofconjugatedpolymersfororganicsolarcellapplicat ions, Chem.Rev., 2009,109,5868; Y.Li, Moleculardesignofphotovoltaicmaterialsforpolymersolarcel ls:towardsuitableelectronicenergylevelsandbroadabsorptio n, Acc.Chem.Res., 2012,45,723; Z.He, C.Zhong, X.Huang, W.Y.Wong, H.Wu, L.Chen, S.Su, Y.Cao, Simultaneousenhancementofopen-circuitvoltage, short-circuitcurrentdensity, andfillfactorinpolymersolarcells, Adv.Mater., 2011,23,4636; Z.C.He, C.M.Zhong, S.J.Su, M.Xu, H.B.Wu, Y.Cao, Enhancedpower-conversionefficiencyinpolymersolarcellsusi nganinverteddevicestructure, Nat.Photonics, 2012,6,591; S.H.Liao, H.J.Jhuo, Y.S.Cheng, S.A.Chen, Fullerenederivative-dopedzincoxidenanofilmasthecathodeof invertedpolymersolarcellswithlow-bandgappolymer (PTB7-Th) forhighperformance, Adv.Mater., 2013,25,4766; V.Gupta, A.K.K.Kyaw, D.H.Wang, S.Chand, G.C.Bazan, A.J.Heeger, Barium:anefficientcathodelayerforbulk-heterojunctionsola rcells, Sci.Rep., 2013,3,1965; W.Li, A.Furlan, K.H.Hendriks, M.M.Wienk, R.A.J.Janssen, Efficienttandemandtriple-junctionpolymersolarcells., J.Am.Chem.Soc., 2013,135,5529; J.Zhou, Y.Zuo, X.Wan, G.Long, Q.Zhang, W.Ni, Y.Liu, Z.Li, G.He, C.Li, B.Kan, M.Li, Y.Chen, Solution-processedandhigh-performanceorganicsolarcellsus ingsmallmoleculeswithabenzodithiopheneunit, J.Am.Chem.Soc., 2013,135,8484.).Up to the present, through optimization to molecular structure, device architecture and complete processing, break through 10% based on polymeric donor or small molecules to the electricity conversion of the solar cell of body and the blended preparation of fullerene acceptor.This demonstrates huge applications prospect (Y.Liu, C.-C.Chen, the Z.Hong of organic solar batteries, J.Gao, Y.Yang, H.Zhou, L.Dou, G.Li, Y.Yang, Solution-processedsmall-moleculesolarcells:breakingthe10 %powerconversionefficiency, Sci.Rep., 2013,3; You, J.; Chen, C.C.; Hong, Z.; Yoshimura, K.; Ohya, K.; Xu, R.; Ye, S.; Gao, J.; Li, G.; Yang, Y.10.2%Powerconversionefficiencypolymertandemsolarcellsc onsistingoftwoidenticalsub-cells, Adv.Mater., 2013,25,3973; J.You, L.Dou, K.Yoshimura, T.Kato, K.Ohya, T.Moriarty, K.Emery, C.-C.Chen, J.Gao, G.Li, Y.Yang, Apolymertandemsolarcellwith10.6%powerconversionefficienc y, Nat.Commun., 2013,4,1446.).Wherein to absorb the scope of sunlight relatively wide due to it for polymer materials, and the electricity conversion of its photovoltaic device is higher.By the optimization to material structure and device architecture, the highest electricity conversion of bibliographical information reaches 10.6%.But polymkeric substance also has self shortcoming, as: the polymolecularity of molecular weight distribution, the problems such as between batch, repeatability is poor, and purifying is difficult.In contrast, Organic micromolecular semiconductor material then shows specific advantages, as the molecular structure determined and molecular weight, high purity and batch stable etc.Thus, the research of recent organic molecule solar cell is gradually in heat.
Developing rapidly compared to donor material, acceptor material is slower development then.In acceptor material, with PC 61bM and PC 71bM is that the fullerene derivate of representative is firmly in occupation of dominant position.This is because PCBM has plurality of advantages, as large electron affinity, the outstanding isotropic electronic transmission performance and (G.Yu such as to be separated of nano-scale can be mixed to form with conjugated polymers donor material, J.Gao, J.C.Hummelen, F.Wudl, A.J.Heeger, Polymerphotovoltaiccells:enhancedefficienciesviaanetwork ofinternaldonor-acceptorheterojunctions, Science, 1995,270,1789; Y.He, Y.Li, Fullerenederivativeacceptorsforhighperformancepolymersol arcells, Phys.Chem.Chem.Phys, 2011,13,1970.T.Liu, A.Troisi, Whatmakesfullereneacceptorsspecialaselectronacceptorsino rganicsolarcellsandhowtoreplacethem, Adv.Mater., 2013,25,1038.).But be that the fullerene derivate of representative also also exists shortcomings with PCBM, as absorb in visible region more weak, be difficult to regulation and control energy level, also have (the P.Sonar such as more difficult that purifies, J.P.F.Lim, K.L.Chan, Organicnon-fullereneacceptorsfororganicphotovoltaics, EnergyEnviron.Sci., 2011,4,1558.).Therefore, the acceptor material of synthesizing new is still necessary very much.
In recent years, people, in order to replace the fullerene acceptor in organic solar batteries, have synthesized a series of new small molecule and the non-soccerballene acceptor material of polymkeric substance.When preparing solar cell from different donor materials is blended, show good performance (X.Zhan, Z.Tan, B.Domercq, Z.An, X.Zhang, S.Barlow, Y.Li, D.Zhu, B.Kippelen, S.R.Marder, Ahigh-mobilityelectron-transportpolymerwithbroadabsorpti onanditsuseinfield-effecttransistorsandall-polymersolarc ells, JAmChemSoc, 2007,129,7246, E.Zhou, J.Cong, Q.Wei, K.Tajima, C.Yang, K.Hashimoto, All-polymersolarcellsfromperylenediimidebasedcopolymers: materialdesignandphaseseparationcontrol, Angew.Chem., Int.Ed., 2011,50,2799, J.T.Y.Cao, T.Lei, J.S.Yuan, J.Y.Wang, J.Pei, Dithiazolyl-benzothiadiazole-containingpolymeracceptors: synthesis, characterization, andall-polymersolarcells, PolymerChemistry, 2013,4,5228, P.Cheng, L.Ye, X.G.Zhao, J.H.Hou, Y.F.Li, X.W.Zhan, Binaryadditivessynergisticallyboosttheefficiencyofall-po lymersolarcellsupto3.45%, EnergyEnviron.Sci., 2014,7,1351, S.Fabiano, S.Himmelberger, M.Drees, Z.Chen, R.M.Altamimi, A.Salleo, M.A.Loi, A.Facchetti, Chargetransportorthogonalityinall-Polymerblendtransistor s, diodes, andsolarcells, Adv.EnergyMater., 2014,4,1301409, H.Huang, N.Zhou, R.P.Ortiz, Z.Chen, S.Loser, S.Zhang, X.Guo, J.Casado, J.T.L ó pezNavarrete, X.Yu, A.Facchetti, T.J.Marks, Alkoxy-functionalizedthienyl-vinylenepolymersforfield-ef fecttransistorsandall-polymersolarcells, Adv.Funct.Mater., 2014, DOI:10.1002/adfm.201303219, W.Li, W.S.Roelofs, M.Turbiez, M.M.Wienk, R.A.Janssen, Polymersolarcellswithdiketopyrrolopyrroleconjugatedpolym ersastheelectrondonorandelectronacceptor, AdvMater, 2014, DOI:10.1002/adma.201305910, W.Yu, D.Yang, X.Zhu, X.Wang, G.Tu, D.Fan, J.Zhang, C.Li, Controlofnanomorphologyinall-polymersolarcellsviaassembl ingnanoaggregationinamixedsolution, ACSApplMaterInterfaces, 2014,6,2350, E.Zhou, J.Cong, K.Hashimoto, K.Tajima, Controlofmiscibilityandaggregationviathematerialdesignan dcoatingprocessforhigh-performancepolymerblendsolarcells, AdvMater, 2013,25,6991, N.Zhou, H.Lin, S.J.Lou, X.Yu, P.Guo, E.F.Manley, S.Loser, P.Hartnett, H.Huang, M.R.Wasielewski, L.X.Chen, R.P.H.Chang, A.Facchetti, T.J.Marks, Morphology-performancerelationshipsinhigh-efficiencyall-polymersolarcells, Adv.EnergyMater., 2014,4,1300785, Y.Z.Lin, Y.F.Li, X.W.Zhan, Asolution-processableelectronacceptorbasedondibenzosilol eanddiketopyrrolopyrrolefororganicsolarcells, Adv.EnergyMater., 2013,3,724, Y.Lin, P.Cheng, Y.Li, X.Zhan, A3Dstar-shapednon-fullereneacceptorforsolution-processed organicsolarcellswithahighopen-circuitvoltageof1.18V, Chem.Commun., 2012,48,4773, J.T.Bloking, X.Han, A.T.Higgs, J.P.Kastrop, L.Pandey, J.E.Norton, C.Risko, C.E.Chen, J.L.Bredas, M.D.McGehee, A.Sellinger, Solution-processedorganicsolarcellswithpowerconversionef ficienciesof2.5%usingbenzothiadiazole/imide-Basedaccepto rs, Chem.Mat., 2011,23,5484, Bloking, T.Giovenzana, A.T.Higgs, A.J.Ponec, E.T.Hoke, K.Vandewal, S.Ko, Z.Bao, A.Sellinger, M.D.McGehee, Comparingthedevicephysicsandmorphologyofpolymersolarcell semployingfullerenesandnon-fullereneacceptors, Adv.EnergyMater., 2014, DOI:10.1002/aenm.201301426, Y.Zhou, L.Ding, K.Shi, Y.Z.Dai, N.Ai, J.Wang, J.Pei, Anon-fullerenesmallmoleculeasefficientelectronacceptorin organicbulkheterojunctionsolarcells, Adv.Mater., 2012,24,957, Y.Q.Zheng, Y.Z.Dai, Y.Zhou, J.Y.Wang, J.Pei, Rationalmolecularengineeringtowardsefficientnon-fulleren esmallmoleculeacceptorsforinvertedbulkheterojunctionorga nicsolarcells, Chem.Commun., 2014,50,1591, G.Q.Ren, E.Ahmed, S.A.Jenekhe, Non-FullereneAcceptor-basedbulkheterojunctionpolymersola rcells:engineeringthenanomorphologyviaprocessingadditive s, Adv.EnergyMater., 2011,1,946, Y.Lin, Y.Wang, J.Wang, J.Hou, Y.Li, D.Zhu, X.Zhan, AStar-shapedperylenediimideelectronacceptorforhigh-perfo rmanceorganicsolarcells, Adv.Mater., 2014, DOI:10.1002/adma.201400525, W.Jiang, L.Ye, X.Li, C.Xiao, F.Tan, W.Zhao, J.Hou, Z.Wang, Bay-linkedperylenebisimidesaspromisingnon-fullereneaccep torsfororganicsolarcells, Chem.Commun., 2014,50,1024, S.Rajaram, R.Shivanna, S.K.Kandappa, K.S.Narayan, Nonplanarperylenediimidesaspotentialalternativestofuller enesinorganicsolarcells, J.Phys.Chem.Lett., 2012,3,2405.), and all-polymer solar cell (D.Mori, H.Benten, I.Okada, H.Ohkita, S.Ito, Low-bandgapdonor/acceptorpolymerblendsolarcellswitheffic iencyexceeding4%, Adv.EnergyMater., 2014,4,1301006, Y.Zhou, T.Kurosawa, W.Ma, Y.Guo, L.Fang, K.Vandewal, Y.Diao, C.Wang, Q.Yan, J.Reinspach, J.Mei, A.L.Appleton, G.I.Koleilat, Y.Gao, S.C.Mannsfeld, A.Salleo, H.Ade, D.Zhao, Z.Bao, Highperformanceall-Polymersolarcellviapolymerside-chaine ngineering, AdvMater, 2014, DOI:10.1002/adma.201306242.) and based on the organic solar batteries (X.Zhang of polymeric donor and the non-fullerene acceptor of small molecules, Z.Lu, L.Ye, C.Zhan, J.Hou, S.Zhang, B.Jiang, Y.Zhao, J.Huang, S.Zhang, Y.Liu, Q.Shi, Y.Liu, J.Yao, Apotentialperylenediimidedimer-basedacceptormaterialforh ighlyefficientsolution-processednon-fullereneorganicsola rcellswith4.03%efficiency, Adv.Mater., 2013, 25, 5791, Z.Lu, B.Jiang, X.Zhang, A.Tang, L.Chen, C.Zhan, J.Yao, Perylene – DiimideBasedNon-fullerenesolarcellswith4.34%efficiencyth roughengineeringsurfacedonor/acceptorcompositions, Chem.Mater., 2014, DOI:10.1021/cm5006339.) electricity conversion all more than 4%.This illustrates, develops high performance non-soccerballene acceptor material and is not only necessary very much, and be very feasible.
Due to the two dimensional structure of its rigidity, the conjugated polymers containing condensed ring unit has very strong intermolecular π-π and interacts, thus can obtain higher carrier mobility; Conjugated polymers electron donor(ED) photovoltaic material based on indacene class seven condensed ring unit shows wider absorption spectrum and higher molar absorption coefficient, therefore for obtaining higher short-circuit current (J during solar cell sC).So far, any document or patent report is had no based on seven and A-D-A conjugation small molecules application in organic solar batteries as electron donor(ED) or electron acceptor material of condensed ring unit.
Based on seven and the constructional feature of condensed ring unit, four substituting groups above it are due to a gathering that can effectively reduce outside conjugate planes between acceptor molecule, and regulating and controlling its energy level by haling electronic unit in the introducing of the two ends of seven and condensed ring unit, can use as electron acceptor(EA).
The present invention utilize have high carrier mobility seven and condensed ring unit as core, oligomerisation 5-membered aromatic heterocycle is bridging unit, what change end draws electronic unit design and synthesis a series of based on seven and the A-D-A conjugated molecule of condensed ring unit, this quasi-molecule has stronger absorption, preferably charge transport properties and suitable electronic level, can be applied to organic solar batteries device as electron donor(ED) or electron acceptor material.
Summary of the invention
An object of the present invention be to provide a class have stronger absorption, higher charge transport properties and suitable electronic level based on seven and the A-D-A conjugated molecule of condensed ring unit.
Two of object of the present invention is to provide a kind of based on seven and the preparation method of A-D-A conjugated molecule of condensed ring unit.
Three of object of the present invention is to provide based on seven and A-D-A conjugated molecule application in organic solar batteries as electron donor(ED) or electron acceptor material of condensed ring unit.
The present invention prepare a series of completely newly, good, the Heat stability is good of solvability based on seven and the A-D-A conjugated molecule of condensed ring unit.Due to seven and the two dimensional structure of condensed ring unit rigidity, what end drew electronic unit hales electronic capability, therefore this quasi-molecule has strong visible absorption ability, high charge transport properties and suitable electronic level, is suitable for being applied to as electron donor(ED) or electron acceptor material preparing organic solar batteries.
By ultimate analysis, nucleus magnetic resonance, the mass spectral characteristi chemical structure of A-D-A conjugated molecule of the present invention, the thermostability of A-D-A conjugated molecule of the present invention is characterized with thermogravimetric analysis, characterize the electrochemical properties of A-D-A conjugated molecule of the present invention with cyclic voltammetric, have studied the photophysical property of A-D-A conjugated molecule of the present invention with ultra-violet absorption spectrum.
Of the present invention based on seven and the A-D-A conjugated molecule of condensed ring unit has following formula:
N is 0 ~ 6;
Z=C, Si or N;
X=O, S or Se;
R 1~ R 3be hydrogen, C independently 1~ C 30alkyl, C 1~ C 30alkoxyl group or 4-alkyl phenyl;
Drawing electron group A is selected from one of following structure:
R in above-mentioned A structure 4for C 1~ C 30alkyl.
Alkyl in described 4-alkyl phenyl is C 1~ C 8alkyl.
Of the present invention based on seven and condensed ring unit A-D-A conjugated molecule in, preferred version is: described n is 0 ~ 3; Described Z=C; X=S; R 1~ R 3be hydrogen, C independently 1~ C 8alkyl or 4-hexyl phenyl; R in A structure 4for C 1~ C 8alkyl.
Of the present invention based on seven and condensed ring unit A-D-A conjugated molecule in, preferred version is: described n is 0 ~ 3; R 1~ R 3be hydrogen, C independently 1~ C 12alkyl, C 1~ C 12alkoxyl group or 4-hexyl phenyl; R in A structure 4for C 1~ C 8alkyl.
Of the present invention based on seven and the preparation method of A-D-A conjugated molecule of condensed ring unit comprise the following steps:
Will with R 1, R 2, R 3substituent seven and condensed ring unit aldehyde compound with draw electronic unit A to join in reaction vessel, wherein: with R 1, R 2, R 3substituent seven and condensed ring unit aldehyde compound with draw the mol ratio of electronic unit A to be 1:2 ~ 100; Take chloroform as solvent, logical rare gas element adds piperidines or pyridine after getting rid of the air in reaction vessel, at temperature is 30 ~ 80 DEG C, carry out stirring reaction; After reaction terminates, pour in methyl alcohol by gained reaction product, filtration drying obtains solid, by chromatography over CC obtain having following formula based on seven and the A-D-A conjugated molecule product of condensed ring unit; Or:
Will with R 1substituent seven and condensed ring unit tin trimethyl compound with R 2, R 3single bromine oligomerisation five-membered aromatic heterocyclic compounds of substituting group and drawing electron group A joins in reaction vessel, wherein: with R 1substituent seven and condensed ring unit tin trimethyl compound with R 2, R 3the mol ratio of single bromine oligomerisation five-membered aromatic heterocyclic compounds of substituting group and drawing electron group A is 1:2 ~ 5; Take toluene as solvent, logical rare gas element adds the tetrakis triphenylphosphine palladium catalyzer of catalytic amount after getting rid of the air in reaction vessel, at temperature is 100 ~ 120 DEG C, carry out stirring reaction; Add after reaction terminates relative to R 1substituent seven potassium fluoride aqueous solutions that also condensed ring unit tin trimethyl compound molar weight is excessive, extraction drying is also filtered, be spin-dried for filtrate and obtain solid, by chromatography over CC obtain having following formula based on seven and the A-D-A conjugated molecule product of condensed ring unit;
N is 0 ~ 6;
Z=C, Si or N;
X=O, S or Se;
R 1~ R 3be hydrogen, C independently 1~ C 30alkyl, C 1~ C 30alkoxyl group or 4-alkyl phenyl;
Drawing electron group A is selected from one of following structure:
R in above-mentioned A structure 4for C 1~ C 30alkyl.
Described piperidines or the add-on of pyridine are described piperidines or pyridine and with R 1, R 2, R 3substituent seven and the mol ratio of condensed ring unit aldehyde compound is 1:0.001 ~ 0.5.
The described time of carrying out stirring reaction at temperature is 30 ~ 80 DEG C is 6 ~ 48 hours.
The preferably described tetrakis triphenylphosphine palladium catalyzer of the add-on of described tetrakis triphenylphosphine palladium catalyzer with R 1substituent seven and the mol ratio of condensed ring unit tin trimethyl compound is 1:10 ~ 100.
The described time of carrying out stirring reaction at temperature is 100 ~ 120 DEG C is 12 ~ 48 hours.
Of the present invention based on seven and the A-D-A conjugated molecule of condensed ring unit has stronger absorption, higher charge transport properties and suitable electronic level, can be used as active coating electron donor(ED) that light catches or electron acceptor material is applied in organic solar batteries.
Major advantage of the present invention is:
1. synthesis based on seven and condensed ring unit A-D-A conjugated molecule can solution method processing, be dissolved in the organic solvents such as methylene dichloride, chloroform, tetrahydrofuran (THF) and chlorobenzene.
2. synthesis based on seven and the A-D-A conjugated molecule Heat stability is good of condensed ring unit, initial heat decomposition temperature is more than 300 DEG C.
3. synthesis based on seven and the A-D-A conjugated molecule light absorptive of condensed ring unit is good, be applicable to doing organic solar battery material.
4. synthesis based on seven and the A-D-A conjugated molecule of condensed ring unit has suitable electronic level, be suitable for the electron donor material in organic solar batteries or electron acceptor material.
5. synthesis based on seven and the A-D-A conjugated molecule of condensed ring unit shows very high electricity conversion as electron donor material or electron acceptor material in organic solar batteries.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 based on seven and the uv-visible absorption spectra of A-D-A conjugated molecule 1 of condensed ring unit.
Fig. 2 be the embodiment of the present invention 1 based on seven and the cyclic voltammetry curve of A-D-A conjugated molecule 1 of condensed ring unit.
Fig. 3 be the embodiment of the present invention 1 based on seven and the thermogravimetric curve of A-D-A conjugated molecule 1 of condensed ring unit.
Fig. 4 be the embodiment of the present invention 2 based on seven and the uv-visible absorption spectra of A-D-A conjugated molecule 2 of condensed ring unit.
Fig. 5 be the embodiment of the present invention 2 based on seven and the cyclic voltammetry curve of A-D-A conjugated molecule 2 of condensed ring unit.
Fig. 6 be the embodiment of the present invention 2 based on seven and the thermogravimetric curve of A-D-A conjugated molecule 2 of condensed ring unit.
Fig. 7 be the embodiment of the present invention 3 based on seven and the uv-visible absorption spectra of A-D-A conjugated molecule 3 of condensed ring unit.
Fig. 8 be the embodiment of the present invention 3 based on seven and the cyclic voltammetry curve of A-D-A conjugated molecule 3 of condensed ring unit.
Fig. 9 be the embodiment of the present invention 3 based on seven and the thermogravimetric curve of A-D-A conjugated molecule 3 of condensed ring unit.
Figure 10 be the embodiment of the present invention 1 based on seven and the I-V curve of organic solar batteries of the A-D-A conjugated molecule 1 of condensed ring unit; Record the short-circuit current J of device scfor 15.89mAcm -2, open circuit voltage V ocfor 0.81V, packing factor FF is 59.2%, effciency of energy transfer PCE is 7.62%.
Figure 11 be the embodiment of the present invention 2 based on seven and the I-V curve of organic solar batteries of the A-D-A conjugated molecule 2 of condensed ring unit; Record the short-circuit current J of device scfor 16.65mAcm -2, open circuit voltage V ocfor 0.93V, packing factor FF is 42.3%, effciency of energy transfer PCE is 6.56%.
Figure 12 be the embodiment of the present invention 3 based on seven and the I-V curve of organic solar batteries of the A-D-A conjugated molecule 3 of condensed ring unit; Record the short-circuit current J of device scfor 12.53mAcm -2, open circuit voltage V ocfor 0.83V, packing factor FF is 60.1%, effciency of energy transfer PCE is 6.25%.
Embodiment
Embodiment 1
Based on seven and the synthetic route of A-D-A conjugated molecule 1 of condensed ring unit is as follows:
In three mouthfuls of round-bottomed flasks, add compound a (200mg, 0.19mmol), compound b (279mg, 1.4mmol), chloroform (50mL), logical argon gas adds 1mL pyridine in 30 minutes after removing the air in three mouthfuls of round-bottomed flasks; At temperature is 65 DEG C, carry out stirring reaction 12 hours, be then cooled to room temperature; Gained reaction solution is poured in 200mL methyl alcohol, filter the precipitation dry rear silica gel (200 ~ 300 order) pillar layer separation that obtain, eluent is sherwood oil/methylene dichloride (volume ratio is 1:1), product is blue solid (57mg, 21%), be based on seven and the A-D-A conjugated molecule 1 of condensed ring unit. 1HNMR(400MHz,CDCl 3):δ8.87(s,2H),8.70(d,J＝7.6Hz,2H),8.22(s,2H),7.93(d,J＝6.4Hz,2H),7.79(m,4H),7.63(s,2H),7.23(d,J＝8.4Hz,8H),7.15(d,J＝8.4Hz,8H),2.58(m,8H),1.61(m,8H),1.33(m,24H),0.87(m,12H). 13CNMR(100MHz,CDCl 3):δ188.18,160.36,155.65,152.86,147.65,147.06,143.64,142.51,140.02,139.60,138.94,138.24,136.95,136.86,135.19,134.49,128.87,127.89,125.32,123.76,122.73,118.53,114.63,114.57,69.38,63.24,35.61,31.70,31.27,29.20,22.59,14.10.MS(MALDI):m/z1427.4(M+1).Anal.CalcdforC 94H 82N 4O 2S 4:C,79.07；H,5.79；N,3.92.Found:C,78.93；H,5.70；N,3.85％。
Based on seven and condensed ring unit A-D-A conjugated molecule 1 uv-visible absorption spectra as shown in Figure 1; Cyclic voltammetry curve as shown in Figure 2; Thermogravimetric curve as shown in Figure 3; The I-V curve of prepared organic solar batteries as shown in Figure 10.
Embodiment 2
Based on seven and the synthetic route of A-D-A conjugated molecule 2 of condensed ring unit is as follows:
Compound c (165mg is added in three mouthfuls of round-bottomed flasks, 0.11mmol), compound b (219mg, 1.1mmol), chloroform (50mL), logical argon gas adds 0.5mL pyridine in 30 minutes after removing the air in three mouthfuls of round-bottomed flasks; At temperature is 65 DEG C, carry out stirring reaction 12 hours, be then cooled to room temperature; Gained reaction solution is poured in 200mL methyl alcohol, filter the precipitation dry rear silica gel (200 ~ 300 order) pillar layer separation that obtain, eluent is sherwood oil/methylene dichloride (volume ratio is 1:1), product is dark green solid (152mg, 74%), be based on seven and the A-D-A conjugated molecule 2 of condensed ring unit. 1HNMR(400MHz,CDCl 3):δ8.78(s,2H),8.70(d,J＝7.2Hz,2H),7.93(d,J＝7.2Hz,2H),7.77(m,4H),7.69(s,2H),7.60(s,2H),7.56(s,2H),7.21(d,J＝8.0Hz,8H),7.14(d,J＝8.0Hz,8H),2.78(d,J＝7.2Hz,4H),2.60(m,8H),1.64(m,14H),1.35(m,36H),0.88(m,24H). 13CNMR(100MHz,CDCl 3):δ118.86,160.76,154.67,150.11,149.50,147.13,146.27,143.47,142.74,140.62,140.50,140.39,137.70,137.38,136.92,136.83,136.52,135.56,134.96,129.30,128.59,125.79,124.28,122.90,121.88,118.02,115.16,69.84,63.64,40.02,36.25,34.73,34.26,33.05,32.33,32.21,31.93,29.82,29.14,26.35,23.58,14.69,11.26.MS(MALDI):m/z1815.6(M+1).Anal.CalcdforC 118H 118N 4O 2S 6:C,78.02；H,6.55；N,3.08.Found:C,77.93；H,6.45；N,3.12％。
Based on seven and condensed ring unit A-D-A conjugated molecule 2 uv-visible absorption spectra as shown in Figure 4; Cyclic voltammetry curve as shown in Figure 5; Thermogravimetric curve as shown in Figure 6; The I-V curve of prepared organic solar batteries as shown in figure 11.
Embodiment 3
Based on seven and the synthetic route of A-D-A conjugated molecule 3 of condensed ring unit is as follows:
In three mouthfuls of round-bottomed flasks, add compound d (200mg, 0.148mmol), Verbindung (100mg, 0.345mmol) and 20mL toluene, logical argon gas adds Pd (PPh to remove the air in three mouthfuls of round-bottomed flasks in 15 minutes 3) 4(40mg, 0.034mmol), carries out stirring reaction 48 hours at temperature is 110 DEG C; Be cooled to room temperature; Add 40mL (0.1gmL -1) the KF aqueous solution, room temperature for overnight, to remove detin impurity; 150mL water is added, CH in gained reactant 2cl 2(2 × 150mL) extracts, the anhydrous MgSO of gained organic phase 4carry out drying; Filter and be spin-dried for except after desolventizing, eluent is made with sherwood oil/methylene dichloride mixed solvent (volume ratio is 1:1), silica gel (200 ~ 300 order) pillar layer separation is purified, obtain black-and-blue solid (30mg, 14.1%), be based on seven and the A-D-A conjugated molecule 3 of condensed ring unit. 1H-NMR(400MHz,CD 2Cl 2):δ8.79(s,2H),8.73(s,2H),8.69(d,J＝8.0Hz,2H),7.92(d,J＝8.0Hz,2H),7.66(s,2H),7.26(d,J＝8.4Hz,8H),7.17(d,J＝8.0Hz,8H),2.60(m,8H),1.56(m,8H),1.27(m,24H),0.85(m,12H).MS(MALDI):m/z1438.6(M+)。
Based on seven and condensed ring unit A-D-A conjugated molecule 3 uv-visible absorption spectra as shown in Figure 7; Cyclic voltammetry curve as shown in Figure 8; Thermogravimetric curve as shown in Figure 9; The I-V curve of prepared organic solar batteries as shown in figure 12.
The preparation and property test of solar photovoltaic device:
Tin indium oxide (ITO) glass that business is bought first is cleaned with cleaning agent, then water, deionized water, acetone, Virahol ultrasonic cleaning successively, the Polyglycolic acid fibre that after dry, spin coating one deck 30nm is thick: poly styrene sulfonate PEDOT:PSS (weight ratio 1:1) (4083) anode modification layer, at 150 DEG C, drying 15 minutes, for subsequent use.By embodiment 1 ~ 3 based on seven and the A-D-A conjugated molecule 1 ~ 3 of condensed ring unit is spun on the blend solution (20 ~ 30mg/ml) of polymer donor material PTB7-TH (weight ratio is all 1:0.5 ~ 4) active coating PEDOT:PSS (4083) anode modification layer being formed device respectively.Photovoltaic device active layer useful area is 4mm 2.Vacuum (3 × 10 on active coating -5pa) metallic aluminium of evaporation thickness about 50nm is as the negative electrode of photovoltaic device.
With being furnished with the Newport500W xenon lamp of AM1.5 spectral filter as simulated solar light source, at 100mW/cm 2carry out photovoltaic performance test to device under light intensity, light intensity is calibrated by standard monocrystalline silicon solar cell; J-V curve uses Keithley236 to measure, and is controlled by computer by Labview software.
Based on seven and the I-V curve of organic solar batteries of the A-D-A conjugated molecule 1 ~ 3 of condensed ring unit as shown in Figure 10 ~ 12.
The structure of the polymeric donor PTB7-TH that the present invention is used is as follows:
。

Claims (10)

1., based on seven and the A-D-A conjugated molecule of condensed ring unit, it is characterized in that, described based on seven and the A-D-A conjugated molecule of condensed ring unit has following formula:
N is 0 ~ 6;
Z=C, Si or N;
X=O, S or Se;
R 1~ R 3be hydrogen, C independently 1~ C 30alkyl, C 1~ C 30alkoxyl group or 4-alkyl phenyl;
Drawing electron group A is selected from one of following structure:
R in above-mentioned A structure 4for C 1~ C 30alkyl.
2. according to claim 1 based on seven and the A-D-A conjugated molecule of condensed ring unit, it is characterized in that: the alkyl in described 4-alkyl phenyl is C 1~ C 8alkyl.
3. according to claim 1 based on seven and the A-D-A conjugated molecule of condensed ring unit, it is characterized in that: described n is 0 ~ 3; Described Z=C; X=S; R 1~ R 3be hydrogen, C independently 1~ C 8alkyl or 4-hexyl phenyl; R in A structure 4for C 1~ C 8alkyl.
4. according to claim 1 based on seven and the A-D-A conjugated molecule of condensed ring unit, it is characterized in that: described n is 0 ~ 3; R 1~ R 3be hydrogen, C independently 1~ C 12alkyl, C 1~ C 12alkoxyl group or 4-hexyl phenyl; R in A structure 4for C 1~ C 8alkyl.
5. described in Claims 1 to 4 any one based on seven and the preparation method of A-D-A conjugated molecule for condensed ring unit, it is characterized in that, described preparation method comprises the following steps:
Will with R 1, R 2, R 3substituent seven and condensed ring unit aldehyde compound with draw electronic unit A to join in reaction vessel, wherein: with R 1, R 2, R 3substituent seven and condensed ring unit aldehyde compound with draw the mol ratio of electronic unit A to be 1:2 ~ 100; Take chloroform as solvent, logical rare gas element adds piperidines or pyridine after getting rid of the air in reaction vessel, at temperature is 30 ~ 80 DEG C, carry out stirring reaction; After reaction terminates, pour in methyl alcohol by gained reaction product, filtration drying obtains solid, by chromatography over CC obtain having following formula based on seven and the A-D-A conjugated molecule product of condensed ring unit; Or:
Will with R 1substituent seven and condensed ring unit tin trimethyl compound with R 2, R 3single bromine oligomerisation five-membered aromatic heterocyclic compounds of substituting group and drawing electron group A joins in reaction vessel, wherein: with R 1substituent seven and condensed ring unit tin trimethyl compound with R 2, R 3the mol ratio of single bromine oligomerisation five-membered aromatic heterocyclic compounds of substituting group and drawing electron group A is 1:2 ~ 5; Take toluene as solvent, logical rare gas element adds the tetrakis triphenylphosphine palladium catalyzer of catalytic amount after getting rid of the air in reaction vessel, at temperature is 100 ~ 120 DEG C, carry out stirring reaction; Add after reaction terminates relative to R 1substituent seven potassium fluoride aqueous solutions that also condensed ring unit tin trimethyl compound molar weight is excessive, extraction drying is also filtered, be spin-dried for filtrate and obtain solid, by chromatography over CC obtain having following formula based on seven and the A-D-A conjugated molecule product of condensed ring unit;
N is 0 ~ 6;
Z=C, Si or N;
X=O, S or Se;
R 1~ R 3be hydrogen, C independently 1~ C 30alkyl, C 1~ C 30alkoxyl group or 4-alkyl phenyl;
Drawing electron group A is selected from one of following structure:
R in above-mentioned A structure 4for C 1~ C 30alkyl.
6. preparation method according to claim 5, is characterized in that: described piperidines or the add-on of pyridine are described piperidines or pyridine and with R 1, R 2, R 3substituent seven and the mol ratio of condensed ring unit aldehyde compound is 1:0.001 ~ 0.5.
7. preparation method according to claim 5, is characterized in that: the described time of carrying out stirring reaction at temperature is 30 ~ 80 DEG C is 6 ~ 48 hours; The described time of carrying out stirring reaction at temperature is 100 ~ 120 DEG C is 12 ~ 48 hours.
8. preparation method according to claim 5, is characterized in that: the add-on of described tetrakis triphenylphosphine palladium catalyzer be described tetrakis triphenylphosphine palladium catalyzer with R 1substituent seven and the mol ratio of condensed ring unit tin trimethyl compound is 1:10 ~ 100.
9. preparation method according to claim 5, is characterized in that: the alkyl in described 4-alkyl phenyl is C 1~ C 8alkyl.
10. described in Claims 1 to 4 any one based on seven and the application of A-D-A conjugated molecule for condensed ring unit, it is characterized in that: described based on seven and the A-D-A conjugated molecule of the condensed ring unit active coating electron donor(ED) of catching as light or electron acceptor material apply in organic solar batteries.
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