CN105153189A - Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof - Google Patents
Narrow-band-gap oligomer containing quinone type Methyl-Dioxocyano-Pyridine unit, and preparation method and application thereof Download PDFInfo
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- 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
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- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/84—Nitriles
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- H10K85/60—Organic compounds having low molecular weight
- H10K85/649—Aromatic compounds comprising a hetero atom
- H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract
The invention discloses a narrow-band-gap oligomer containing a quinone type Methyl-Dioxocyano-Pyridine unit, and a preparation method and application thereof. The oligomer has a structural general formula as shown in a formula I. The narrow-band-gap oligomer is a solution-processible electron donor type small organic molecule. The invention also provides a method for synthesizing narrow-band-gap oligomers. Meanwhile, the narrow-band-gap oligomer is used as an electron donor for preparation of an organic solar cell by combining with electron acceptor derivatives like PC71BM, has high photoelectric conversion efficiency, and provides a novel direction for research in the field of photovoltaic industry.
Description
Technical field
The invention belongs to organic photovoltaic Material Field, relate to a kind of narrow band gap oligomer containing quinoid Methyl-Dioxocyano-Pyridine unit and preparation method thereof and application.
Background technology
Along with the develop rapidly of economy, environmental problem and energy dilemma become increasingly conspicuous.Organic solar batteries, as a kind of effective means utilizing sun power, obtains and studies widely.Small molecules solar cell is with its accurate molecular structure, and repeatable, the advantage of easy purifying has attracted increasing concern.The solar cell of traditional soccerballene base, the main donor material that leans on absorbs photon that is visible and near infrared region, this is because fullerene derivate ([6,6]-phenyl-C
61-butyricacidmethylester, is called for short PC
61bM and [6,6]-phenyl-C
71-butyricacidmethylester, is called for short PC
71bM) absorption mainly concentrates on UV, visible light region.And in solar spectrum, the solar photon more than 50% is distributed in wavelength 600-1000nm place, the wavelength region that wherein photon stream is the strongest is 600-800nm.Catch this part sunlight in order to as much as possible, be necessary that development is at visible ray, near infrared even infrared region has strong narrow band gap (<1.6eV, the i.e. energy of absorption edge >800nm) molecule absorbed.
At present, donor-π-acceptor, i.e. D-π-A concept are the most frequently used methods of constructing low bandgap material.This method is in most cases the π bridge by a conjugation, connects one to electronic unit and an electrophilic unit.Widely usedly comprise oligo-thiophenes (formula 1) to electronic unit, benzene 1,4-Dithiapentalene (being called for short BDT, formula 2), silicon is coughed up (P. such as (formulas 3)
etal.Adv.Mater.2006,18,2872; X.Feng, etal.J.Mater.Chem.2011,21,17590; L.Dai, etal.Adv.Mater.2011,23,4554; J.Hou, etal.Angew.Chem.Int.Ed.2011,50,9697; A.J.Heeger, etal.Sci.Rep.2013,3,01965).Comprise pyrrolo-pyrrole-dione (being called for short DPP, formula 4) by body unit, benzo dithiazole (is called for short BT, formula 5), (R.A.Janssen such as fluorine boron two pyrroles (being called for short BODIPY, formula 6), etal.J.Am.Chem.Soc.2013,135,18942; G.C.Bazan, etal.ACSnano2013,7,4569-4577; C.L.Zhan, etal.ACSAppl.Mater.Interfaces2014,6,22496.).In the donor material reported at present, the film absorption of the material of DPP base is extended to 700-750nm (T.J.Marks, etal., J.Am.Chem.Soc.2011,133,8142.), silicon coughs up the absorbed of the A-D-A type of base more than 800nm (A.J.Heeger, etal.Sci.Rep.2013,3,01965.).What is interesting is, the energy of absorption edge that two alpha-positions put the donor material of the BODIPY that π expands can extend to 900nm (C.L.Zhan, etal.ACSAppl.Mater.Interfaces2014,6,22496.).
BDT unit outstanding gives electronic unit as one, is widely used in the design of donor material.Such as, utilize its as give electronic unit, DPP can close to 6% as the device efficiency of the molecule DPP-BDT-DPP that electrophilic unit is constructed, this is also efficiency (C.L.Zhan the highest in current DPP base small molecules, etal.ACSAppl.Mater.Interfaces2013,5,2033; X.W.Zhan, etal.Adv.EnergyMater.2013,3,1166; C.L.Zhan, etal.Adv.EnergyMater.2015, DOI:10.1002/aenm.201500059.).In addition, research shows the donor monomer of BDT as centre, rhodanine molecule is as the electrophilic unit at two ends, both connect by terthienyl the molecule obtained as conjugated bridge, the band edge of its film absorption is at about 700nm (Y.Chen, etal.J.Am.Chem.Soc.2013,135,8484.).When utilizing indandione to substitute rhodanine unit as electrophilic unit, connect two thiophene as conjugated bridge, the band edge of the film absorption of the molecule obtained can red shift to 750nm (Y.Li, etal.Chem.Mater.2013,25,2274.).
Comprise electrophilic cyano group and imide structure in Methyl-dioxocyano-pyridine (MDP) unit, therefore there is strong electron-withdrawing power.Draw electronic effect because it is strong, contribute to forming strong intramolecular transfer transport, reduce lowest unoccupied molecular orbital (LUMO) energy level of material, form narrow band gap.Meanwhile, in the cyanine dyes of D-A type, the quinoid structure inducing molecule skeleton of MDP has the exchange that very large trend takes π-electron, makes cyanine dyes take zwitterionic structure (K.Meerholz, etal.Adv.Mater.2010,22,4193; F.W ü rthner, etal.Chem.Mater.2014,26,4856.).These features make cyanine dyes intramolecule there is strong push-and-pull electronic effect, and π-electron delocalization in convenient formation molecule also provides the cyclic voltammetry method absorption band of red shift (H.W.A.Lademann, etal.Chem.Commun.2008,6489 by force; F.W ü rthner, etal.J.Mater.Chem.2010,20,240.).Quinoid is resonant is a kind of resonance form under polymer materials ground state.Quinoid is resonant has lower energy relative to direction structure, and the ratio therefore improving quinoid resonant contributes to providing low energy level.A classical example, namely the aromaticity of thiophene unit is lower than phenyl ring, and therefore it more easily takes quinoid structure.Result is exactly the energy level of Polythiophene is 2.0eV, be starkly lower than 3.2eV (J.Qin, etal.Chem.Mater.2014,26,3495 of polyphenyl ring; F.Wudl, etal.J.Chem.Phys.1986,85,4673.).
Summary of the invention
The object of this invention is to provide a kind of narrow band gap oligomer containing quinoid Methyl-Dioxocyano-Pyridine unit and preparation method thereof and application.
Narrow band gap oligomer containing quinoid Methyl-Dioxocyano-Pyridine unit provided by the invention, its general structure such as formula shown in I,
In described formula I, R
1be selected from C
mh
2m+1alkyl and C
mh
2m+1alkoxyl group in any one, m is the integer of 1-20;
R
2be selected from hydrogen atom and C
mh
2m+1any one of alkyl, m is the integer of 1-20;
R
3be selected from C
mh
2m+1alkyl, m is the integer of 1-20;
X be selected from sulphur atom, selenium atom and Sauerstoffatom any one; ;
Y is selected from Sauerstoffatom, sulphur atom, carbon atom, 2-thienyl, 2-furyl, 2-selenophen base, 2-connect in dithienyl, 2-1,4-Dithiapentalene base and a position (m)-phenyl, contraposition (p)-phenyl any one;
N is the integer of 0-10.
In described formula I, m is the integer of 1-10, is specially the integer of 2-8;
N specifically can be 0-8 integer, is more specifically the integer of 0-5, more specifically can be 0,1,2,3,4 or 5;
Described C
mh
2m+1alkyl be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, 2-methyl butyl, 2-methyl amyl, 2-methylhexyl, 2-methyl-heptyl, 2-ethyl propyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl and 2-propylpentyl any one;
Described C
mh
2m+1alkoxyl group be selected from methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy, octyloxy, 2-methyl pentyloxy, 2-ethyl pentyloxy, 2-ethyl-butoxy, 2-methylbutoxy group and 2-ethyl hexyl oxy any one.
Concrete, described R
1can be positioned at described benzo dithienyl phenyl on, preferably, described R
1replacement position be preferably contraposition on phenyl and/or a position.
Described
specifically be selected from following group any one:
Wherein, R=-C
nh
2n+1, n is the integer of 1-12.
Concrete, described oligomer be selected from following compound any one:
Shown in the described formula I of preparation provided by the invention, the method for oligomer, comprises the steps:
Compound shown in compound and formula IV shown in formula II is carried out Knoevenagel condensation reaction, reacts complete and obtain oligomer shown in described formula I;
In described formula II and formula IV, R
1, R
2, R
3, X, Y be all identical with the definition in described formula I with the definition of n.
In aforesaid method, described Knoevenagel condensation reaction is carried out in organic solvent;
Described organic solvent is specifically selected from least one in chloroform and acetic anhydride, is more specifically selected from least one in anhydrous chloroform and Glacial acetic acid acid anhydride, the mixed solution be most preferably obtained by mixing by anhydrous chloroform and Glacial acetic acid acid anhydride;
In described mixed solution, the volume ratio of anhydrous chloroform and Glacial acetic acid acid anhydride is 2-10:10, is specially 10:10;
Shown in described formula II, the molar ratio of compound shown in compound and formula IV is 1:5-10, specifically can be 1:5,1:6,1:8;
The amount ratio of compound and acetic anhydride shown in described formula II is 1mmol:50mL;
In the anti-reactions steps of described Knoevenagel condensation, temperature is 70-120 DEG C, is specially 100-110 DEG C; Time is 6-15 hour, is specially 12 hours.
Described method also comprises the steps: in described step 3) after, purification process is carried out to reaction system;
Described purification process is poured in ethanol, suction filtration after specifically comprising the steps: that reaction completes, with ethanol, and washing twice, the solid obtained, crosses post with silica gel and obtains oligomer shown in the described formula I after purifying;
Wherein, the consumption of described ethanol is 30-100mL, specifically can be 50-60mL; Used silica gel specifically can be H60 silica gel; Crossing post solvent for use specifically can for the mixed solution be made up of methylene dichloride and ethyl acetate, and its ratio can be determined according to the polarity of product, and the volume ratio as methylene dichloride and ethyl acetate can be 10-50:1, specifically can be 20:1,30:1.
In addition, in oligomer shown in above-mentioned preparation formula I, shown in reaction raw materials formula II used, compound also belongs to protection scope of the present invention.Compound shown in this formula II can obtain according to the method preparation comprised the steps:
Two for benzene 1,4-Dithiapentalene shown in bromo-for 2-shown in formula III 5 formylthiophene compounds and formula a tin trimethyl compound is reacted under the existence of catalyzer and organic solvent, obtains compound shown in described formula II;
The equation of this reaction is as follows:
Shown in above-mentioned preparation formula II, the method for compound specifically can be prepared as follows and obtain: be dissolved in dry toluene by bromo-for 2-shown in formula III 5 formylthiophene compounds, adds the two tin trimethyl compound of the benzene of compound shown in formula a 1,4-Dithiapentalene and tetrakis triphenylphosphine palladium (Pd (PPh
3)
4), react complete and obtain compound shown in described formula II;
In aforesaid method, described catalyzer specifically can be tetrakis triphenylphosphine palladium (Pd (PPh
3)
4; Described organic solvent specifically can be toluene, more specifically can be dry toluene; In described reactions steps, the time of reaction is the time is 12-48 hour; Temperature is 90-120 DEG C, is specially 110 DEG C;
The molar ratio of the two tin trimethyl compound of benzene 1,4-Dithiapentalene shown in the bromo-5 formylthiophene compounds of 2-shown in described formula III and formula a is 2-4:1;
The 1%-20% that the consumption of described catalyzer is the mole dosage that feeds intake of the bromo-5 formylthiophene compounds of 2-shown in described formula III, preferably 17%;
The amount ratio of the bromo-5 formylthiophene compounds of 2-shown in described organic solvent and formula III is 5-80mL:1mmol.
According to the present invention, after step (1) reaction, purification process is carried out to reaction system.
Described purification process specifically comprises the steps: the toluene underpressure distillation removing in reaction system, gained mixed solution is dissolved in the mixed solvent be made up of methylene dichloride and water, separatory collects dichloromethane layer, after organic phase anhydrous magnesium sulfate carries out drying, underpressure distillation removing methylene dichloride obtains mixture, crosses post obtain oligomer shown in the described formula II after purifying with silica gel;
Wherein, in the described mixed solvent be made up of methylene dichloride and water, the volumetric usage of methylene dichloride and water is 30-100mL, specifically can be 50-60mL; Used silica gel specifically can be H60 silica gel; Crossing post solvent for use specifically can for the mixed solution be made up of methylene dichloride and sherwood oil, and its ratio can be determined according to the polarity of product, as can be 3:1.
In oligomer shown in above-mentioned preparation formula I, shown in reaction raw materials formula IV used, compound also belongs to protection scope of the present invention.Compound shown in this formula IV can obtain according to the method preparation comprised the steps:
Ethyl cyanacetate, alkylamine, methyl aceto acetate are reacted in organic solvent, reacts complete and obtain compound shown in described formula IV;
The equation of this reaction is as follows:
Compound shown in described formula IV specifically can obtain according to the method preparation comprised the steps: at 0 DEG C, by ethyl cyanacetate and R
3nH
2shown alkylamine mixing, reaction rises to room temperature, reacts after 1 hour-6 hours, methyl aceto acetate and hexahydropyridine is joined respectively in reaction system, is warming up to 25-120 DEG C of reaction 1-15 hour, obtains compound shown in described formula IV;
Wherein, described R
3nH
2in shown alkylamine, R
3definition and formula I in R
3definition identical;
In aforesaid method, described organic solvent specifically can six hydrogen piperidines;
The amount ratio of described ethyl cyanacetate, alkylamine, methyl aceto acetate and organic solvent is 1mmol:1mmol-2mmol:1mmol-2mmol:0.01-2mL;
Describedly be warming up in 25-120 DEG C of reactions steps, the preferred 80-120 DEG C of temperature, more preferably 90-120 DEG C, most preferably 110 DEG C; Reaction times specifically can be 4-12 hour, preferred 8-10 hour, more preferably 9 hours.
Described method also comprises the steps: to be warming up to 25-120 DEG C of reaction after 1-15 hour described, carries out purification process to reaction system;
Described purification process specifically comprises the steps: that the pH value of reaction system is adjusted to pH=1 by the HCl aqueous solution with mass percentage concentration is 32%, and gained is precipitated suction filtration, with water and ether cleaning twice, dry and obtain.
In addition; oligomer shown in the formula I that the invention described above provides is at the application prepared in solar cell and the solar cell containing oligomer shown in formula I; and oligomer, preparing the application in solar cell photovoltaic active coating, also belongs to protection scope of the present invention shown in this formula I.
The present invention is the claimed composition for the preparation of solar cell photovoltaic active coating also, and said composition comprises oligomer shown in aforementioned formula I provided by the invention.
Wherein, receptor type polymkeric substance is also comprised in described solar cell;
Receptor type polymkeric substance is also comprised in described composition;
Described receptor type polymkeric substance is specifically selected from PC
61bM, PC
71at least one in BM, indene-C60bisadduct (ICBA) and indene-C60monoadduct (ICMA);
Above-mentioned PC
61bM, PC
71the structural formula of BM, indene-C60bisadduct (ICBA) and indene-C60monoadduct (ICMA) is as follows successively:
Described solar cell is made up of ITO, hole transmission layer, ITO, photovoltaic active layers, electronics abstraction, layer and electrode;
Wherein, the material forming described electrode layer is ITO;
The material forming described hole transmission layer is PEDOT:PSS;
Form the material of described photovoltaic active layers for oligomer shown in described formula I and described receptor type polymkeric substance;
The material forming electronics abstraction, layer be selected from calcium and PDINO any one;
The material forming described electrode be selected from aluminium, gold and silver any one;
Described ITO is ito glass electrode, can be directly commercially available, and the width of ITO specifically can be 0.3nm;
The thickness of described hole transmission layer is 10nm-50nm, preferred 30nm-35nm;
The thickness of described photoactive layer is 50nm-200nm, preferred 100nm-150nm;
The thickness of described electronics abstraction, layer is 10nm-30nm, preferred 20nm-25nm;
The thickness of described electrode is 70nm-100nm, preferred 80nm;
Concrete, described solar cell can obtain according to the method preparation comprised the steps:
1) in an inert atmosphere, after oligomer shown in formula I and described receptor type polymkeric substance are dissolved 4-10 hour in organic solvent, spin coating liquid is obtained;
2) by step 1) gained spin coating liquid is coated in the surface of ITO/PEDOT:PSS, obtains described photovoltaic active layers;
3) in step 2) methanol solution of evaporation layer of metal calcium or spin coating PDINO on gained photovoltaic active layers, obtain electronics abstraction, layer, then evaporation metal aluminium or gold or silver, as electrode, obtain described solar cell in gained electronics abstraction, layer;
Described step 1) in, organic solvent is specifically selected from least one in dichlorobenzene, chloroform and chlorobenzene;
The mass parts of oligomer shown in described formula I is 1-5 part, is specially 1-3 part;
The mass parts of described receptor type polymkeric substance is 1-10 part, is specially 1-3 part;
In described spin coating liquid, oligomer shown in described formula I and the total concn of described receptor type polymkeric substance in described spin coating liquid are 8-15mg/mL20-30mg/mL or 30-40mg/mL;
In addition, the above-mentioned method preparing solar cell also comprises the steps:
In described step 1) before dissolving step, in system, add 1,8-diiodo-octane; Described 1, the 8-diiodo-octane concentration expressed in percentage by volume accounted in described spin coating liquid is 0.1% ~ 10%;
In described step 2) after, step 3) before, rear thermal annealing is dried in the spin coating of gained photoactive layer; In described thermal anneal step, the temperature of annealing is specially 80-100 DEG C, and the time is specially 5-10min.
Described step 3) in, PDINO is aminoN-oxideperylenediimide, and Chinese standardize naming is amino N-Yangization perylene diimides; The methanol solution of described PDINO can obtain from following document: J.Wang, etal.EnergyEnviron.Sci.2014,7, (6), 1966.
The invention provides a kind of MDP-π-BDT-π-MDP base narrow band gap oligomer of the symmetry containing quinoid Methyl-Dioxocyano-Pyridine unit, and provide a kind of novel method of synthesizing this kind of narrow band gap oligomer.MDP-π-BDT-π-MDP base narrow band gap the oligomer of this symmetry is the machinable electron donating type organic molecule of solution, can combine with electron acceptor(EA) type derivatives such as PC61BM or PC71BM that sell on market, for organic photovoltaic battery device, be applied to optoelectronic areas.The electric current that MDP-π-BDT-π-MDP base narrow band gap oligomer of the present invention produces can reach 14.38mA/cm
2, photoelectric transformation efficiency can reach 6.3%.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum that bromo-5 aldehyde radicals of 2-connect two thiophene (interior) (compd B r-2T (in)-CHO).
Fig. 2 is the nucleus magnetic hydrogen spectrum that bromo-5 aldehyde radicals of 2-connect two thiophene (outward) (compd B r-2T (out)-CHO).
Fig. 3 is the nucleus magnetic hydrogen spectrum that embodiment 1 prepares gained BDT-CHO.
Fig. 4 is the nucleus magnetic hydrogen spectrum that embodiment 2 prepares gained BDT-1T-CHO.
Fig. 5 is the nucleus magnetic hydrogen spectrum that embodiment 3 prepares gained MDP.
Fig. 6 is nucleus magnetic hydrogen spectrum (a) and carbon spectrum (b) that embodiment 4 prepares gained 3TBM.
Fig. 7 is that embodiment 4 prepares gained compound 3TBM organic solar batteries device photovoltaic graphic representation.
Fig. 8 is that embodiment 4 prepares gained compound 5TBM organic solar batteries device photovoltaic graphic representation.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
The preparation method that bromo-5 aldehyde radicals of compound 2-shown in following embodiment formula III used connect two thiophene (interior) (compound 2T (in)) is as follows:
The bromo-3-octyl thiophene (275mg, 1mmol) of 2-, 3-octyl group-2-thienyl boric acid ester (322mg, 1mmol), 2.0MK
2cO
3aqueous solution 2ML, THF (15mL) join in reaction flask.Pd (PPh is added after mixture bubbling argon deoxygenation 20min
3)
4(30mg).Use bubbling argon deoxygenation 10min post-heating to 80 DEG C again, under condition of nitrogen gas, stir 8h.After reaction terminates, be cooled to room temperature, carry out separatory process with methylene dichloride and water.After organic phase anhydrous magnesium sulfate carries out drying, solvent evaporated, residue silica gel column chromatography is separated.Leacheate is sherwood oil, obtains yellow oil 2T (in) (332mg, 84.5%).
1hNMR (400MHz, CDCl
3, δ): 7.29-7.28 (d, J=4Hz, 2H), 6.97-6.96 (d, J=4Hz, 2H), 2.52-2.47 (t, 4H), 1.52-1.56 (m, 4H), 1.22-1.27 (m, 20H), 0.85-0.90 (m, 6H).
At-78 DEG C, under argon shield, joined by above-claimed cpd 2T (in) (392mg, 1mmol) in the super dry THF of 10mL, n-BuLi (2.5MinTHF, 1mL, 2.50mmol) dropwise adds wherein.At this temperature, stir 1 hour, oxygen pentaborane (0.5mL, 2.5mmol) of being mixed by 2-isopropoxy-4,4,5,5-tetramethyl--1,3,2-bis-afterwards adds wherein, and at room temperature stirs 12 hours.After reaction terminates, evaporate to dryness organic solvent, residue with Ethyl acetate and the process of moisture liquid, organic phase anhydrous magnesium sulfate carries out drying, without being further purified, directly uses.
The preparation of Vilsmeierreagent, by POCl
3(0.17mL, 1.9mmol) dropwise joins in DMF (10mL), reaction.Afterwards by obtained Vilsmeierreagent (0.6mL) in argon shield, join under-78 DEG C of conditions in the solution of 1,2-dichloroethane (10mL) of 2T (in) (334mg, 1mmol).Be heated to 70 DEG C afterwards and stir 12h, in mixture impouring frozen water (100mL), use Na
2cO
3neutralize, methylene dichloride extracts.The anhydrous MgSO of organic phase
4dry.Finally use petroleumether:DCM (4:1) to carry out column chromatographic isolation and purification as leacheate, obtain 2T (in)-CHO (289mg, 79.4%).
1hNMR (400MHz, CDCl
3, δ): 9.86 (s, 1H), 7.64 (s, 1H), 7.35-7.36 (d, J=4Hz, 1H), 6.99-6.98 (d, J=4Hz, 1H), 2.47-2.56 (t, 4H), 1.52-1.57 (m, 4H), 1.22-1.30 (m, 20H), 0.85-0.88 (m, 6H).
By 2T (in)-CHO (418g, 1mmol) be dissolved in trichloromethane, afterwards under lucifuge condition by N-bromosuccinimide (196g, 1.1mmol) join several times in this solution, stirring at room temperature is after 6 hours, reactant methylene dichloride and water carry out separatory extraction, organic phase anhydrous magnesium sulfate carries out drying, after solvent evaporated, methylene dichloride and sherwood oil (1:6) carry out column chromatography separating purification as leacheate, obtain yellow oil (472mg, 95%).
1hNMR (400MHz, CDCl
3, δ): 9.86 (s, 1H), 7.62 (s, 1H), 6.97-6.95 (s, 1H), 2.43-2.56 (t, 4H), 1.48-1.55 (m, 4H), 1.22-1.33 (m, 20H), 0.84-0.89 (m, 6H).
The nucleus magnetic hydrogen spectrum of this product as shown in Figure 1.As from the foregoing, this compound structure is correct, is 5-formyl-5 '-bromo-3,3 '-dioctyl-2,2 '-bithiophene (compd B r-2T (in)-CHO).
The preparation method that bromo-5 aldehyde radicals of compound 2-shown in following embodiment formula III used connect two thiophene (outward) (compound 2T (out)) is as follows:
The bromo-3-octyl thiophene (1.21g, 4.4mmol) of 2-, PdCl
2(PhCN)
2(15.5mg, 0.040mmol), Potassium monofluoride (511mg, 8.8mmol), DMSO (20mL) joins in reaction flask, AgNO afterwards
3(1.49g, 8.8mmol) adds and is warming up to 60 DEG C, heated and stirred 3h.Afterwards, AgNO
3(1.49g, 8.8mmol) and Potassium monofluoride (511mg, 8.8mmol) are adding in above-mentioned reaction solution, continue heated and stirred 3 hours.Reaction mixture sherwood oil carries out column chromatogram chromatography as leacheate, obtains 964mg product 2Br-2T (out) (82%).
1hNMR (400MHz, CDCl
3, δ): 6.77 (s, 2H), 2.48-2.53 (t, 4H), 1.59-1.62 (m, 4H), 1.30-1.27 (m, 20H), 0.86-0.90 (m, 6H).
Under argon shield condition; by 5; 5 '-dibromo-4; 4 '-dioctyl-2; 2 '-bithiophene (548mg, 1mmol) (2Br-2T (out)) is dissolved in the super dry THF of 10mL, by n-BuLi (2.5MinTHF under the condition of-78 DEG C; 0.4mL, 1mmol) dropwise join in this solution.Mixture stirs 2 hours at this temperature, is added wherein by Dimethylformamide (DMF) (0.1mL, 1.1mmol) afterwards and at room temperature stir to spend the night.After reaction terminates, carry out separatory process with methylene dichloride and water, organic phase anhydrous magnesium sulfate carries out drying, solvent evaporated.Use methylene dichloride and sherwood oil (1:7) to carry out column chromatography purification as leacheate afterwards, obtain yellow oil (251mg, 51%).
1HNMR(400MHz,CDCl
3,δ):9.98(s,1H),7.02(s,1H),6.97(s,1H),2.88-2.94(t,2H),2.52-2.57(t,2H),1.59-1.70(m,4H),1.25-1.31(m,20H),0.84-0.90(m,6H).
The nucleus magnetic hydrogen spectrum of this product as shown in Figure 2.As from the foregoing, this compound structure is correct, is 5-formyl-5 '-bromo-4,4 '-dioctyl-2,2 '-bithiophene (compd B r-2T (in)-CHO).
Compd B DT-CHO shown in embodiment 1, preparation formula II
Under argon shield condition; by 4; 8-bis (5-ethylhexylthiophen-2-yl) benzo-[1; 2-b:4; 5-b '] dithiophene (245mg, 0.5mmol) is dissolved in the super dry THF of 10mL, by n-BuLi (2.5Minhexane under the condition of-78 DEG C; 0.44mL, 1.1mmol) dropwise join in this solution.Mixture stirs 1 hour at this temperature, is added wherein by Dimethylformamide (DMF) (0.1mL, 1.1mmol) afterwards and at room temperature stir to spend the night.After reaction terminates, be poured in water, carry out extraction treatment with methylene dichloride, organic phase anhydrous magnesium sulfate carries out drying, solvent evaporated.Use methylene dichloride and sherwood oil (3:1) to carry out column chromatography purification as leacheate afterwards, obtain safran solid (1.22g, 90%).
1hNMR (400MHz, CDCl
3, δ): 10.10 (s, 2H), 8.36 (s, 2H), 7.34-7.35 (d, J=4Hz, 2H), (6.94-6.95 d, J=4Hz, 2H), (2.88-2.89 d, J=4Hz, 4H), 1.68-1.71 (m, 2H), 1.22-1.30 (m, 16H), 0.94-0.99 (m, 12H).
The nucleus magnetic hydrogen spectrum of this product as shown in Figure 3.As from the foregoing, this compound structure is correct, is 2,6-diformyl-4,8-bis (5-ethylhexylthiophen-2-yl) benzo-[1,2-b:4,5-b '] dithiophene (compd B DT-CHO).
Compd B DT-1T-CHO shown in embodiment 2, preparation formula II
Under argon shield; by the Br-1T-CHO (76mg of ownership formula III; 0.25mmol), 2 of formula a is belonged to; 6-bis-(tin trimethyl)-4; 8 (5-diethylhexyl-thienyl) benzene 1,4-Dithiapentalene (90.4mg; 0.1mmol), super dry toluene (20mL) mixing loads in reaction flask, afterwards by Pd (PPh
3)
4(20mg, 0.017mmol) adds, and continues to advertise argon gas 20 minutes post-heating to 110 DEG C, stirs 12h.After reaction terminates, be cooled to room temperature, by the toluene underpressure distillation removing in reaction system, gained mixed solution is dissolved in the mixed solvent be made up of methylene dichloride and water, separatory collects dichloromethane layer, after organic phase anhydrous magnesium sulfate carries out drying, underpressure distillation removing methylene dichloride obtains mixture, crossing post with H60 silica gel, to obtain purifying leacheate be methylene dichloride/sherwood oil (3:1, v/v), carry out recrystallization with trichloromethane and methyl alcohol, obtain safran solid product (86.7mg, 85%).
1hNMR (400MHz, CDCl
3, δ): 9.85 (s, 2H), 7.82 (s, 2H), 7.61 (s, 2H), 7.33-7.34 (d, J=4Hz, 2H), 6.91-6.92 (d, J=4Hz, 2H), 2.84-2.89 (t, 8H), 1.64-1.71 (m, 6H), 1.22-1.30 (m, 36H), 0.85-0.89 (m, 18H).
The nucleus magnetic hydrogen spectrum of this product as shown in Figure 4.As from the foregoing, this compound structure is correct, is compd B DT-1T-CHO.
Compound 4-methyl-dioxocyano-pyridine shown in embodiment 3, preparation formula IV (MDP)
At 0 DEG C, in 15 minutes, ethyl cyanacetate (2mL, 18mmol) is joined in 2 ethyl hexylamine (2.7mL, 18.8mmol), is slowly warming up to room temperature, stir 6 hours.Afterwards methyl aceto acetate (2.4mL, 18.8mmol) and hexahydropyridine (0.5mL) are dropwise joined in reaction solution, be warming up to 110 DEG C, reflux 9 hours.After reaction terminates, be down to room temperature, with the HCl aqueous solution of 32%, reactant be adjusted to pH=1, the precipitation suction filtration obtained, with water and ether cleaning twice, drying for standby, obtains the MDP of 3.7 grams, and productive rate is 80%.
1HNMR(400MHz,DMSO-d
6,δ):5.59(s,1H),3.78-3.83(m,2H),2.21(s,3H),1.75-1.78(m,1H),1.18-1.26(m,8H),0.85-0.89(m,6H).
The nucleus magnetic hydrogen spectrum of this product as shown in Figure 5.As from the foregoing, this compound structure is correct, is compound MDP.
Compound nTBM shown in embodiment 4, preparation formula I
Preparation 0TBM
bDT-CHO (0.1mmol), MDP (79mg, 0.3mmol) join chloroform and diacetyl oxide (1:1 that cumulative volume is 10mL, V/V), in solution, backflow (100-110 DEG C) is carried out Knoevenagel condensation reaction and is spent the night (being also 12 hours).After having reacted, pour in ethanol, suction filtration, with ethanol, washing twice, the solid obtained, carries out H60 purification by silica gel column chromatography, and leacheate is methylene dichloride: ethyl acetate (50:1, V/V), obtaining target product is dark green solid (67mg, 60%yield).
1HNMR(400MHz,CDCl
3,δ):8.31(s,2H),7.90(s,2H),7.41-7.42(d,J＝4Hz,2H),6.99-7.00(d,J＝4Hz,2H),3.92-3.94(m,4H),2.91-2.93(m,4H),2.64(s,6H),1.71-1.83(m,4H),1.28-1.37(m,36H),0.89-0.98(m,24H).
13CNMR(100MHz,CDCl
3,δ):162.78,160.60,157.92,147.69,144.47,142.21,141.18,137.68,134.93,129.50,126.19,125.97,121.23,114.51,106.44,44.19,41.73,37.76,34.59,32.84,30.74,29.17,28.64,25.94,24.06,23.27,23.23,19.05,14.39,14.31,11.14,10.64.MALDI-TOF(m/z):[M+H]
+calcdforC
66H
82N
4O
4S
4,1123.64；found,1122.6.Anal.calcdforC
66H
82N
4O
4S
4:C70.55,H7.36,N4.99；found:C70.51,H7.40,N4.92.
The nucleus magnetic hydrogen spectrum of this product and carbon spectrum are as shown in figure 6 a and 6b.As from the foregoing, this compound structure is correct, is compound 0TBM.
1TBM
leacheate is methylene dichloride: ethyl acetate (40:1, V/V), and obtaining target product is black solid (98mg, 65%).
1hNMR (400MHz, CDCl
3, δ): 7.94 (s, 2H), 7.85 (s, 2H), 7.63 (s, 2H), 7.38-7.39 (d, J=4Hz, 2H), 6.94-6.95 (d, J=4Hz, 2H), 3.92-3.96 (m, 4H), 2.88-2.90 (m, 8H), 2.64 (s, 6H), 1.86 (m, 2H), 1.68-1.70 (m, 6H), 1.29-1.40 (m, 52H), 0.89-0.98 (m, 30H).
13cNMR (100MHz, CDCl
3,δ): 163.40,160.98,158.16,148.79,148.14,146.80,143.97,142.32,140.18,137.68,137.00,136.48,136.45,128.40,125.89,124.58,117.36,115.07,104.49,44.19,41.68,37.65,34.52,32.79,32.09,30.68,30.43,29.75,29.61,29.55,29.48,29.14,28.62,25.92,24.11,23.27,23.23,22.89,19.09,14.35,14.30,11.09,10.81.MALDI-TOF (m/z): [M+H]
+calcdforC
90h
118n
4o
4s
6, 1512.31; Found, 1511.2.Anal.calcdforC
90h
118n
4o
4s
6: C71.48, H7.86, N3.70; Found:C71.42, H7.92, N3.65.
2T (in) BM
leacheate is methylene dichloride: ethyl acetate (30:1, V/V), and obtaining target product is black solid (114mg, 62%).
1hNMR (400MHz, CDCl
3, δ): 7.82 (s, 2H), (7.59-7.60 d, J=4Hz, 4H), (7.25-7.26 d, J=4Hz, 2H), (7.15 s, 2H), 6.86-6.87 (d, J=4Hz, 2H), 3.82-3.89 (m, 4H), 2.81-2.82 (m, 4H), (2.50-2.60 m, 16H), 1.76-1.77 (m, 2H), 1.61-1.65 (m, 2H), (1.53 m, 8H), 1.17-1.29 (m, 64H), 0.75-0.91 (m, 36H).
13cNMR (100MHz, CDCl
3,δ): 163.06,160.83,158.09,147.94,146.57,146.21,144.43,144.17,143.63,138.99,138.76,137.51,137.00,136.75,127.99,127.95,127.51,125.58,123.73,119.66,117.22,114.89,104.44,44.12,41.58,37.56,34.44,32.64,31.92,31.88,30.75,30.64,29.49,29.40,29.37,29.24,29.03,28.64,28.56,25.93,23.96,23.11,23.09,22.69,18.91,14.20,14.11,11.01,10.62.HRMS (ESI) m/z:[M+H]
+calcdforC
21h
38n
4o
6s, 475.2591; Found, 475.2593.Anal.calcdforC
45h
28n
4o
7: C62.47, H3.41, N6.78; Found:C62.27, H3.46, N6.80.
2T (out) BM
leacheate is methylene dichloride: ethyl acetate (30:1, V/V), and obtaining target product is black solid (111mg, 60%).
1hNMR (400MHz, CDCl
3, δ): 8.02 (s, 2H), (7.74 s, 2H), 7.42 (s, 1H), 7.35-7.36 (d, J=4Hz, 2H), 7.24 (s, 2H), (6.93-6.94 d, J=4Hz, 2H), (3.96-3.98 m, 4H), 2.83-2.89 (m, 12H), 2.63 (s, 6H), (1.88-1.91 m, 2H), 1.65-1.70 (m, 8H), 1.28-1.40 (m, 78H), 0.85-0.97 (m, 36H).
13cNMR (100MHz, CDCl
3,δ): 163.34, 161.09, 160.51, 158.35, 151.47, 146.11, 142.63, 140.28, 139.03, 136.99, 136.64, 136.52, 134.83, 134.52, 131.21, 130.52, 127.96, 126.91, 125.53, 123.49, 122.09, 115.27, 114.96, 102.79, 43.97, 41.52, 37.47, 34.33, 32.57, 31.94, 31.84, 31.71, 30.53, 30.45, 29.88, 29.72, 29.61, 29.48, 29.43, 29.36, 29.21, 28.96, 28.48, 27.22, 25.73, 23.93, 23.15, 23.09, 22.72, 22.65, 18.86, 14.85, 14.56, 11.01, 10.56.MALDI-TOF (m/z): [M+H]
+calcdforC
114h
154n
4o
4s
8, 1900.99, found, 1900.3.Anal.calcdforC
114h
154n
4o
4s
8: C72.03, H8.17, N2.95, found:C71.98, H8.11, N2.91.
3TBM
leacheate is trichloromethane, and obtaining target product is black solid (148mg, 72%).
1hNMR (400MHz, CDCl
3, δ): 7.81 (s, 2H), 7.62 (s, 2H), 7.58 (s, 1H), 7.46-7.47 (d, J=4Hz, 2H), 7.33-7.34 (d, J=4Hz, 2H), 7.17-7.18 (d, J=4Hz, 2H), 7.13 (s, 2H), 6.95-6.96 (d, J=4Hz, 2H), 3.94-3.97 (m, 4H), (2.77-2.93 m, 12H), 2.62 (s, 6H), 1.86-1.89 (m, 2H), (1.66-1.74 m, 10H), 1.28-1.42 (m, 72H), 0.85-0.99 (m, 36H).
13cNMR (100MHz, CDCl
3,δ): 163.20, 161.42, 158.42, 148.46, 146.34, 143.81, 141.63, 140.71, 139.62, 139.03, 137.53, 135.08, 133.98, 130.55, 135.05, 129.08, 128.77, 128.15, 126.82, 125.67, 123.53, 119.58, 116.57, 115.31, 114.77, 103.83, 44.19, 41.68, 37.68, 34.59, 32.77, 32.07, 30.73, 30.62, 30.26, 29.98, 29.90, 29.86, 29.78, 29.73, 29.65, 29.59, 29.53, 29.45, 29.12, 28.67, 27.42, 26.09, 24.12, 23.30, 23.28, 22.87, 19.08, 14.42, 14.34, 14.30, 11.20, 10.82.MALDI-TOF (m/z): [M+H]
+calcdforC
122h
158n
4o
4s
10, 2065.63, found, 2065.4.Anal.calcdforC
122h
158n
4o
4s
10: C70.95, H7.71, N2.71, found:C70.90, H7.78, N2.64.
4T (in) BM
leacheate is methylene dichloride: ethyl acetate (20:1, V/V), and obtaining target product is black solid (161mg, 60%).
1hNMR (400MHz, CDCl
3, δ): 7.85 (s, 2H), (7.60-7.63 d, 4H), 7.41 (s, 1H), 7.33-7.34 (d, J=4Hz, 2H), 7.13 (s, 2H), (7.05 s, 2H), 6.93-6.94 (d, J=4Hz, 2H), 3.94-3.96 (m, 4H), 2.77-2.93 (m, 12H), 2.34-2.64 (s, 16H), 1.25-1.74 (m, 130H), 0.85-0.99 (m, 48H).
13cNMR (100MHz, CDCl
3,δ): 163.45, 161.15, 158.05, 149.68, 148.35, 146.25, 143.92, 143.48, 140.76, 140.71, 139.00, 137.93, 137.87, 137.05, 135.35, 135.02, 134.92, 132.65, 131.18, 130.27, 129.95, 128.59, 128.00, 127.87, 127.80, 125.60, 127.73, 119.22, 116.68, 115.04, 103.98, 44.20, 40.75, 37.75, 34.61, 32.81, 32.03, 30.84, 30.69, 30.31, 30.18, 29.65, 29.64, 29.63, 29.56, 29.38, 29.20, 28.71, 28.65, 26.15, 24.14, 23.21, 22.79, 18.85, 14.26, 14.17, 11.12, 10.75.MALDI-TOF (m/z): [M+H]
+calcdforC
162h
226n
4o
4s
12, 2678.33, found, 2677.4.Anal.calcdforC
162h
226n
4o
4s
12: C72.65, H8.51, N2.09, found:C72.59, H8.63, N2.02.
4T (out) BM
leacheate is methylene dichloride: ethyl acetate (30:1, V/V), and obtaining target product is black solid (166mg, 62%).
1hNMR (400MHz, CDCl
3, δ): 7.89 (s, 2H), (7.67 s, 2H), 7.64 (s, 2H), 7.31-7.32 (d, J=4Hz, 2H), 7.17 (s, 2H), (7.07-7.09 d, J=8Hz, 4H), (6.92-6.93 d, J=4Hz, 2H), (3.88-3.94 m, 4H), 2.88-2.90 (m, 4H), 2.51-2.69 (m, 22H), 1.24-1.71 (m, 132H), 0.82-0.97 (m, 48H).
13cNMR (100MHz, CDCl
3,δ): 163.15, 160.92, 158.22, 148.52, 146.85, 146.12, 144.41, 144.32, 143.77, 143.54, 138.76, 138.72, 137.86, 137.42, 137.32, 136.93, 136.79, 136.54, 128.80, 128.01, 127.88, 127.01, 126.42, 125.81, 125.73, 125.57, 123.50, 119.10, 116.99, 115.01, 104.22, 44.09, 41.56, 37.53, 34.42, 32.61, 31.96, 30.82, 30.66, 30.61, 30.55, 29.49, 29.45, 29.41, 29.30, 29.11, 29.04, 28.67, 28.56, 25.89, 23.92, 23.14, 22.74, 19.00, 14.26, 14.18, 11.03, 10.63.MALDI-TOF (m/z): [M+H]
+calcdforC
162h
226n
4o
4s
12, 2678.33, found, 2677.4.Anal.calcdforC
162h
226n
4o
4s
12: C72.65, H8.51, N2.09, found:C72.61, H8.57, N2.05.
5TBM
leacheate is methylene dichloride: ethyl acetate (10:1, V/V), and obtaining target product is black solid (184mg, 65%).
1hNMR (400MHz, CDCl
3, δ): 7.83 (s, 2H), 7.62 (s, 2H), 7.59 (s, 2H), (7.37 s, 2H), 7.31-7.32 (d, J=4Hz, 2H), 7.17-7.18 (d, 2H), 7.12-7.13 (m, 4H), (7.00 s, 2H), 6.92-6.93 (d, J=4Hz, 2H), 3.88-3.96 (m, 4H), 2.78-2.92 (m, 20H), (2.63 s, 6H), 1.24-1.71 (m, 132H), 0.82-0.97 (m, 48H).
13cNMR (100MHz, CDCl
3,δ): 163.31, 160.97, 157.99, 148.44, 148.33, 148.22, 146.10, 143.72, 140.79, 140.68, 140.62, 140.41, 138.82, 137.71, 137.49, 136.92, 135.17, 135.86, 134.53, 134.24, 131.50, 131.35, 131.06, 130.36, 128.92, 128.42, 127.89, 126.80, 126.19, 125.53, 123.44, 119.11, 116.39, 115.05, 103.67, 44.05, 41.61, 37.61, 34.49, 32.67, 31.94, 30.65, 30.59, 30.50, 30.09, 29.66, 29.58, 29.51, 29.46, 29.37, 29.32, 28.55, 26.00, 24.07, 23.22, 22.70, 18.88, 14.21, 14.15, 14.10, 11.04, 10.69.MALDI-TOF (m/z): [M+H]
+calcdforC
170h
230n
4o
4s
14, 2842.58, found, 2841.5.Anal.calcdforC
170h
230n
4o
4s
14: C71.83, H8.16, N1.97, found:C71.78, H8.23, N1.91.
Embodiment 5, compound 3TBM organic solar batteries device and opto-electronic conversion performance thereof
The modification of ITO electrode: ito glass is after liquid detergent water, water, deionized water, acetone, Virahol ultrasonic cleaning, UVO process 1h is carried out with UV-ozone generating unit, spin coating gathers p styrene sulfonic acid/poly-ethylenedioxythiophene (PEDOT:PSS) aqueous solution again, finally at 150 DEG C, dries 30min.
The preparation of organic solar batteries device A: take compound 3TBM and PC that embodiment 4 prepares by the weight ratio of 1:1
71bM, add the dry chloroform solvent of the excess of imports after mixing to dissolve, add the 1.8-diiodo-octane (DIO) of 1.2% as additive, the active coating mixing solutions of obtained 12mg/mL, stir 4 hours at 60 DEG C, this mixing solutions is spin-coated on the ito glass after PEDOT:PSS modification and prepares active coating film, after active coating dries, at 100 DEG C, carry out thermal annealing 10min.Then be 5 × 10 in vacuum tightness
-5under the condition of Pa, be respectively the calcium of 20nm and the aluminium electrode of 80nm by vacuum-deposited mode evaporation thickness, prepare the photovoltaic cell that area is 2mm*3mm.
The photovoltaic performance of this device shows as: at simulated solar irradiation (AM1.5,100mw/cm
2) under irradiation, produce photoelectric conversion, the current-voltage curve tested as shown in Figure 7, battery performance: open circuit voltage V
oc=0.80V, short-circuit current J
sc=13.81mA/cm
2, packing factor FF=0.546, calculating photoelectric transformation efficiency is 6.03%.
The preparation of organic solar batteries device B: take compound 3TBM and PC that embodiment 4 prepares by the weight ratio of 1:1
71bM, add the dry chloroform solvent of the excess of imports after mixing to dissolve, add the 1.8-diiodo-octane (DIO) of 1.2% as additive, the active coating mixing solutions of obtained 12mg/mL, stir 4 hours at 60 DEG C, this mixing solutions is spin-coated on the ito glass after PEDOT:PSS modification and prepares active coating film, after active coating dries, at 100 DEG C, carry out thermal annealing 10min.On active coating, the active coating solution of spin coating PDINO prepares electrode modification layer afterwards, is then 5 × 10 in vacuum tightness
-5under the condition of Pa, be the aluminium electrode of 80nm by vacuum-deposited mode evaporation thickness, prepare the photovoltaic cell that area is 2mm*3mm.
The photovoltaic performance of this device shows as: at simulated solar irradiation (AM1.5,100mw/cm
2) under irradiation, produce photoelectric conversion, the current-voltage curve tested as shown in Figure 7, battery performance: open circuit voltage V
oc=0.79V; Short-circuit current J
sc=14.38mA/cm
2; Packing factor FF=0.554; Photoelectric transformation efficiency is 6.29%.
Embodiment 6, compound 5TBM organic solar batteries device and opto-electronic conversion performance thereof
The modification of ITO electrode is with embodiment 5.
The preparation of organic solar batteries device A: take compound 5TBM and PC that embodiment 4 prepares by the weight ratio of 1:1.5
71bM, add the dry chloroform solvent of the excess of imports after mixing to dissolve, add the 1.8-diiodo-octane (DIO) of 0.2% as additive, the active coating mixing solutions of obtained 10mg/mL, stir 4 hours at 60 DEG C, being spin-coated on by this mixing solutions on the ito glass after PEDOT:PSS modification and preparing active coating film, after active coating dries, is 5 × 10 in vacuum tightness
-5under the condition of Pa, be respectively the calcium of 20nm and the aluminium electrode of 80nm by vacuum-deposited mode evaporation thickness, prepare the photovoltaic cell that area is 2mm*3mm.
The photovoltaic performance of this device shows as: at simulated solar irradiation (AM1.5,100mw/cm
2) under irradiation, produce photoelectric conversion, the current-voltage curve tested as shown in Figure 8, battery performance: open circuit voltage V
oc=0.78V, short-circuit current J
sc=9.79mA/cm
2, packing factor FF=0.660, calculating photoelectric transformation efficiency is 5.04%.
The preparation of organic solar batteries device B: take compound 5TBM and PC that embodiment 4 prepares by the weight ratio of 1:1.5
71bM, add the dry chloroform solvent of the excess of imports after mixing to dissolve, add the 1.8-diiodo-octane (DIO) of 0.2% as additive, the active coating mixing solutions of obtained 10mg/mL, stir 4 hours at 60 DEG C, this mixing solutions is spin-coated on the ito glass after PEDOT:PSS modification and prepares active coating film, after active coating dries, on active coating, the active coating solution of spin coating PDINO prepares electrode modification layer, is then 5 × 10 in vacuum tightness
-5under the condition of Pa, be the aluminium electrode of 80nm by vacuum-deposited mode evaporation thickness, prepare the photovoltaic cell that area is 2mm*3mm.
The photovoltaic performance of this device shows as: at simulated solar irradiation (AM1.5,100mw/cm
2) under irradiation, produce photoelectric conversion, the current-voltage curve tested as shown in Figure 8, battery performance: open circuit voltage V
oc=0.81V; Short-circuit current J
sc=9.62mA/cm
2; Packing factor FF=0.687; Photoelectric transformation efficiency is 5.35%.
Claims (10)
1. oligomer shown in formula I,
In described formula I, R
1be selected from C
mh
2m+1alkyl and C
mh
2m+1alkoxyl group in any one, m is the integer of 1-20;
R
2be selected from hydrogen atom and C
mh
2m+1any one of alkyl, m is the integer of 1-20;
R
3be selected from C
mh
2m+1alkyl, m is the integer of 1-20;
X be selected from sulphur atom, selenium atom and Sauerstoffatom any one; ;
Y is selected from Sauerstoffatom, sulphur atom, carbon atom, 2-thienyl, 2-furyl, 2-selenophen base, 2-connect in dithienyl, 2-1,4-Dithiapentalene base and a position (m)-phenyl, contraposition (p)-phenyl any one;
N is the integer of 0-10.
2. oligomer according to claim 1, is characterized in that: in described formula I, and m is the integer of 1-10, is specially the integer of 2-8;
N is the integer of 0-8, is specially the integer of 0-5;
Described C
mh
2m+1alkyl be selected from methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, 2-methyl butyl, 2-methyl amyl, 2-methylhexyl, 2-methyl-heptyl, 2-ethyl propyl, 2-ethyl-butyl, 2-ethyl pentyl group, 2-ethylhexyl and 2-propylpentyl any one;
Described C
mh
2m+1alkoxyl group be selected from methoxyl group, oxyethyl group, propoxy-, butoxy, hexyloxy, octyloxy, 2-methyl pentyloxy, 2-ethyl pentyloxy, 2-ethyl-butoxy, 2-methylbutoxy group and 2-ethyl hexyl oxy any one;
Described
be selected from following group any one:
Wherein, R=-C
nh
2n+1, n is the integer of 1-12;
Described oligomer be specifically selected from following compound any one:
3. prepare a method for oligomer shown in arbitrary described formula I in claim 1-2, comprise the steps:
Compound shown in compound and formula IV shown in formula II is carried out Knoevenagel condensation reaction, reacts complete and obtain oligomer shown in described formula I;
In described formula II and formula IV, R
1, R
2, R
3, X, Y be all identical with the definition in formula I described in claim 1 with the definition of n.
4. method according to claim 3, is characterized in that: described Knoevenagel condensation reaction is carried out in organic solvent;
Described organic solvent is specifically selected from least one in chloroform and acetic anhydride, is more specifically selected from least one in anhydrous chloroform and Glacial acetic acid acid anhydride, the mixed solution be most preferably obtained by mixing by anhydrous chloroform and Glacial acetic acid acid anhydride;
In described mixed solution, the volume ratio of anhydrous chloroform and Glacial acetic acid acid anhydride is 2-10:10, is specially 10:10;
Shown in described formula II, the molar ratio of compound shown in compound and formula IV is 1:5-10;
The amount ratio of compound and acetic anhydride shown in described formula II is 1mmol:50mL;
In described Knoevenagel step of condensation, temperature is 70-120 DEG C, is specially 100-110 DEG C; Time is 6-15 hour, is specially 12 hours.
5. in claim 1-2, shown in arbitrary described formula I, oligomer is preparing the application in solar cell; Or,
In claim 1-2, shown in arbitrary described formula I, oligomer is preparing the application in solar cell photovoltaic active coating; Or,
Solar cell containing oligomer shown in described formula I arbitrary in claim 1-2; Or,
For the preparation of a composition for solar cell photovoltaic active coating, comprise oligomer shown in arbitrary described formula I in claim 1-2.
6. application according to claim 5 or solar cell, is characterized in that: also comprise receptor type polymkeric substance in described solar cell;
Receptor type polymkeric substance is also comprised in described composition;
Described receptor type polymkeric substance is specifically selected from PC
61bM, PC
71at least one in BM, ICBA and ICMA:
Described solar cell is specifically made up of ITO, hole transmission layer, photovoltaic active layers, electronics abstraction, layer and electrode;
Wherein, the material forming described hole transmission layer is PEDOT:PSS;
Form the material of described photovoltaic active layers for oligomer and described receptor type polymkeric substance shown in described formula I arbitrary in claim 1-2;
The material forming electronics abstraction, layer be selected from calcium and PDINO any one;
The material forming described electrode be selected from aluminium, gold and silver any one;
The thickness of described hole transmission layer is 10nm-50nm, preferred 30nm-35nm;
The thickness of described photoactive layer is 50nm-200nm, preferred 100nm-150nm;
The thickness of described electronics abstraction, layer is 10nm-30nm, preferred 20nm-25nm;
The thickness of described electrode is 70nm-100nm, preferred 80nm;
Described solar cell specifically obtains according to the method preparation comprised the steps:
1) in an inert atmosphere, after oligomer shown in described formula I arbitrary in claim 1-2 and described receptor type polymkeric substance are dissolved 4-10 hour in organic solvent, spin coating liquid is obtained;
2) step 1) gained spin coating liquid is coated in the surface of ITO/PEDOT:PSS, obtains described photovoltaic active layers;
3) in step 2) methanol solution of evaporation layer of metal calcium or spin coating PDINO on gained photovoltaic active layers, obtain electronics abstraction, layer, then evaporation metal aluminium or gold or silver, as electrode, obtain described solar cell in gained electronics abstraction, layer;
In described step 1), organic solvent is specifically selected from least one in dichlorobenzene, chloroform and chlorobenzene;
The mass parts of oligomer shown in described formula I is 1-5 part, is specially 1-3 part;
The mass parts of described receptor type polymkeric substance is 1-10 part, is specially 1-3 part;
In described spin coating liquid, oligomer shown in described formula I and the total concn of described receptor type polymkeric substance in described spin coating liquid are 8-15mg/mL, 20-30mg/mL or 30-40mg/mL;
And/or described method also comprises the steps:
Before described step 1) dissolving step, in system, add 1,8-diiodo-octane; Described 1, the 8-diiodo-octane concentration expressed in percentage by volume accounted in described spin coating liquid is 0.1% ~ 10%;
In described step 2) after, before step 3), rear thermal annealing is dried in the spin coating of gained photoactive layer; In described thermal anneal step, the temperature of annealing is specially 80-100 DEG C, and the time is specially 5-10min.
7. compound shown in formula II,
In described formula II, R
1, R
2, R
3, X, Y be all identical with the definition in formula I described in claim 1 with the definition of n.
8. prepare a method for compound described in formula II described in claim 7, comprise the steps:
Compound shown in compound and formula a shown in formula III is reacted under the existence of catalyzer and organic solvent, reacts complete and obtain compound shown in described formula II;
Described catalyzer is specially tetrakis triphenylphosphine palladium;
Described organic solvent is specially toluene, is more specifically dry toluene;
In described reactions steps, the time of reaction is specially 12 hours-48 hours; Temperature is specially 90-120 DEG C;
The molar ratio of compound shown in described formula III and formula a institute compound is specially 2-4mmol:1mmol;
The consumption of described catalyzer is specially the 1%-10% of the mole dosage that feeds intake of compound shown in described formula III;
The amount ratio of the bromo-5 formylthiophene compounds of 2-shown in described organic solvent and formula III is specially 5-80mL:1mmol.
9. compound shown in formula IV,
In described formula IV, R
1, R
2, R
3, X, Y be all identical with the definition in formula I described in claim 1 with the definition of n.
10. prepare a method for compound shown in formula IV described in claim 9, comprise the steps: at 0 DEG C, by ethyl cyanacetate and R
3nH
2shown alkylamine mixing, reaction rises to room temperature, reacts after 1 hour-6 hours, methyl aceto acetate and organic solvent is joined respectively in reaction system, is warming up to 25-120 DEG C of reaction 1-15 hour, obtains compound shown in described formula IV;
Wherein, described R
3nH
2in shown alkylamine, R
3definition identical with the definition in formula I described in claim 1;
Described organic solvent is specially six hydrogen piperidines;
The amount ratio of described ethyl cyanacetate, alkylamine, methyl aceto acetate and organic solvent is specially 1mmol:1mmol-2mmol:1mmol-2mmol:0.01-2mL;
Describedly be warming up in 25-120 DEG C of reactions steps, temperature is specially 80-120 DEG C; Reaction times is specially 4-12 hour.
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