CN102807579B - Quinacridone derivative boric acid ester and preparation method thereof and application - Google Patents
Quinacridone derivative boric acid ester and preparation method thereof and application Download PDFInfo
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Abstract
The invention discloses a kind of quinacridone derivative boric acid ester and preparation method thereof and application.This quinacridone derivative boric acid ester is such as formula shown in I.The present invention designs first, synthesized quinacridone boric acid ester, by itself and common acceptor unit process, obtains small molecules and polymer application in organic solar batteries and field-effect transistor.Boric ester derivative provided by the invention is that the small molecules of monomer and polymer molecule planarity are good, in conventional organic solvent, solubleness is large, solution processable, film-forming properties is better, can be used as the photoactive layer material in organic solar batteries and the charge transport layer materials in organic field effect tube, the solar cell energy open circuit voltage of preparation is large, and transformation efficiency is higher, field-effect transistor mobility is high, air-stable.
Description
Technical field
The invention belongs to organic photoelectrical material technical field, be specifically related to quinacridone derivative boric acid ester and preparation method thereof and application.
Background technology
Compared with traditional inorganic photoelectric device, organic electro-optic device has that cost is low, quality is light, easily processing, can prepare the advantages such as large area flexible device, becomes study hotspot in recent years.The structure of organic molecule determines the performance of photoelectric device to a great extent, thus designs, the molecule of composite structure and excellent performance is most important.Organic molecule is applied to solar cell must have wider absorption band, at utmost can absorb sunlight; Secondly molecule has good planarity, crystallinity, effective carrier transport passage (Ergang W. could be formed, Zai F.M., Zhen Z., Koen V., Patrik H., Olle I., Feng L.Z., Mats R.A.J.Am.Chem.Soc.2011,133,14244 – 14247); Finally, molecule will have good solubility, is easy to the preparation and fabrication of solar cell.Organic molecule be applied to field-effect transistor must have low cost, easily film forming, can compatible with flexible substrate, be applicable to feature (the Yuning L. such as machining at low temperature, Samarendra P.S., Prashant S.Adv.Mater.2010,22,4862 – 4866).At present, for the molecule of organic solar batteries and organic field effect tube mainly based on containing the small molecules or the polymkeric substance that connect the monomers such as thiophene, thiophthene, pyrrolopyrrole, diazosulfide, these molecular structures are easily modified, prepare simple, solar cell transformation efficiency and field-effect mobility higher, but these achievements and the market requirement still have gap, the molecule thus preparing textural property more excellent becomes study hotspot.
Quinacridone monomer has larger two dimensional structure, easily modification, easily crystallization, be used to the photoelectric device such as Organic Light Emitting Diode, organic solar batteries in recent years, Jean M.J.Frechet etc. are with quinacridone and the diazosulfide small molecules that has been monomer synthesize, solar cell transformation efficiency is 2.22%(Applied Materials & interfaces2010,2,26792686).Kazuo Takimiya etc. are by quinacridone and thiophene polymeric, and the polymer hole mobility obtained reaches 0.2 (Chem.Mater.2012,24,1235-1243).But current quinacridone is especially that the polymkeric substance application in the opto-electronic device of unit is also few with quinacridone, mainly because the more difficult stannane of quinacridone or acid esterification, limit it not by stille coupling or Suzuki linked reaction and the reaction of most of aromatics bromide.
Summary of the invention
The object of this invention is to provide a kind of quinacridone derivative boric acid ester and preparation method thereof and application.
Quinacridone derivative boric acid ester provided by the invention is also compound shown in formula I,
Formula I
In described formula I, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one.
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR '; In described-COOR', R' is C
1-C
20alkyl or NH
2;
Described R
1be specially 2-octyl group-dodecyl or decyl.
The method of compound shown in the above-mentioned formula I of preparation provided by the invention, comprise the steps: under catalyzer and weak base existent condition, in inert atmosphere, compound shown in formula C is mixed with connection pinacol borate and carries out Suzuki linked reaction, react complete and obtain compound shown in described formula I;
Formula C
In described formula C, R
1and R
2definition with define in formula I identical.
Described catalyzer is selected from 1, at least one in 1 '-[two (diphenylphosphine) ferrocene] palladium chloride, dichloro two triphenylphosphine palladium and four triphenyl phosphorus palladiums;
Described weak base is selected from least one in Potassium ethanoate, salt of wormwood and sodium carbonate;
Described reaction is carried out in a solvent; Described solvent is selected from Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) and N, at least one of N-METHYLFORMAMIDE; Solvent load is as the criterion with complete solubilizing reaction thing;
The mass ratio of compound shown in described pinacol borate, catalyzer, weak base and formula C is 0.3-0.8:0.04-0.08:0.03-0.06:1, preferred 0.6:0.07:0.04:1;
In described Suzuki linked reaction step, temperature is 60-100 DEG C, preferably 80 DEG C, and the time is 10-24 hour, preferably 18 hours;
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere.
In aforesaid method, the B of formula shown in formula C and propane dinitrile heated overnight at reflux and obtaining, concrete preparation process reference Adv.Energy Mater., 2011, Isosorbide-5-Nitrae 31 in solution of acetic anhydride;
Formula B(is R wherein
1definition as hereinbefore) reacted under mildly acidic conditions by formula A and bromine and obtained;
(the wherein R of compound shown in formula A
1definition as hereinbefore) be containing in highly basic, phase-transfer catalyst, toluene system, quinacridone and R
1-Br reaction and obtaining, the concrete preparation process of A, B can reference: Appliedmaterials & interfaces, 2010,2,2679.
Formula A
Formula B
Present invention also offers compound described in formula II,
Formula II
In described formula II, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR '; In described-COOR', R' is C
1-C
20alkyl or NH
2;
Ar is selected from
in at least one;
Described R is H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one
X is S, O or N;
M and n is the integer of 0-5.
The method of compound shown in preparation formula II provided by the invention, comprise the steps: under inert atmosphere and catalyzer existent condition, Suzuki linked reaction is carried out in the mixing of compound shown in compound and Br-Ar described in weak alkaline aqueous solution, formula I, reacts complete and obtain compound shown in described formula II;
In described Br-Ar, the definition of Ar with define in formula II identical.
In aforesaid method, described catalyzer is selected from tetra-triphenylphosphine palladium, 1, at least one in 1 '-[two (diphenylphosphine) ferrocene] palladium chloride and dichloro two triphenylphosphine palladium;
Described weak base is selected from least one in salt of wormwood, potassiumphosphate, Potassium ethanoate and sodium-acetate;
Described Br-Ar is specially
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere;
The concentration of the aqueous solution of described weak base is 0.5-3.0mol/L, preferred 2mol/L
Described in described catalyzer, weak base, bromide Br-Ar and formula I, the mass ratio of compound is 0.05-0.1:0.05-0.09:1.5-2.5:1, preferred 0.06:0.07:1.8:1;
In described Suzuki linked reaction step, temperature is 70-120 DEG C, preferably 110 DEG C, and the time is 10-24 hour, preferably 20 hours;
Described Suzuki linked reaction is carried out in a solvent; Described solvent is selected from least one in toluene, tetrahydrofuran (THF) and DMF.
Present invention also offers alternating copolymer shown in formula III,
Formula III
In described formula III, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR';
R' is C
1-C
20alkyl or NH
2;
The integer that n ' is 7-50, is preferably 10-30;
Ar ＇ is:
Described R is H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one;
X is S, O or N;
M and n is the integer of 0-5.
The method of polymkeric substance shown in the described formula III of preparation provided by the invention, comprise the steps: under inert atmosphere and catalyzer existent condition, after Suzuki polyreaction is carried out in compound shown in the aqueous solution of weak base, described formula I, two bromine substituent Br-Ar'-Br, phase-transfer catalyst mixing, after cooling and phenylo boric acid or 2-boric acid thiophene carry out Suzuki linked reaction after carry out Suzuki coupling end capping with bromobenzene or 2-bromo thiophene again, react complete and obtain polymkeric substance shown in described formula III;
In described Br-Ar'-Br, the definition of Ar' is identical with formula III.
In aforesaid method, described catalyzer is selected from tetra-triphenylphosphine palladium, 1, at least one in 1 '-[two (diphenylphosphine) ferrocene] palladium chloride and dichloro two triphenylphosphine palladium;
Described weak base is selected from least one in salt of wormwood, potassiumphosphate, Potassium ethanoate and sodium-acetate;
Described phase-transfer catalyst is methyl tricapryl ammonium chloride Aliquit336, and structural formula is
Can be bought by his approach of open business and obtain;
Described couple of bromine substituent Br-Ar'-Br is specially
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere;
The concentration of the aqueous solution of described weak base is 0.5-3mol/L, preferred 2mol/L;
Described in described catalyzer, weak base, Aliquat336, two bromine substituent Br-Ar'-Br and formula I, the mass ratio of compound is 0.05-0.1:0.05-0.09:0.001-0.01:0.8-1.6:1, preferred 0.06:0.07:0.005:1.1:1;
In described Suzuki polymerization procedure, temperature is 80-130 DEG C, preferably 110 DEG C, and the time is 36-78 hour, preferably 72 hours;
Described Suzuki polyreaction is carried out in a solvent; Described solvent is selected from least one in toluene, tetrahydrofuran (THF) and DMF;
Described in described phenylo boric acid or 2-boric acid thiophene, bromobenzene or 2-bromo thiophene and claim 1, the mass ratio of compound is 0.002-0.05:0.002-0.05:1, is preferably 0.004:0.004:1;
In described Suzuki coupling end capping step, temperature is 80-130 DEG C, preferably 110 DEG C, and the time is 5-10 hour, preferably 6 hours;
In addition; the organic solar batteries of compound shown in the formula I provided containing the invention described above, formula II and formula III or organic field effect tube; the organic solar batteries being photoactive layer with compound shown in above-mentioned formula I provided by the invention, formula II and formula III or the organic field effect tube for charge transport layer; preparing the application in organic solar batteries or organic field effect tube; in the photoactive layer preparing organic solar batteries or the application prepared in the charge transport layer of organic field effect tube, also belong to protection scope of the present invention.
The present invention designs first, synthesized quinacridone derivative boric acid ester, by itself and common acceptor unit process, obtains small molecules and polymer application in organic solar batteries and field-effect transistor.Boric ester derivative provided by the invention is that the small molecules of monomer and polymer molecule planarity are good, in conventional organic solvent, solubleness is large, solution processable, film-forming properties is better, can be used as the photoactive layer material in organic solar batteries and the charge transport layer materials in organic field effect tube, the solar cell energy open circuit voltage of preparation is large, and transformation efficiency is higher, field-effect transistor mobility is high, air-stable.
Accompanying drawing explanation
Fig. 1 is organic solar energy cell structure schematic diagram
Fig. 2 is the I-V curve of organic solar batteries embodiment 5
Fig. 3 is organic field effect tube structural representation
Fig. 4 is transition curve and the curve of output of organic field effect tube embodiment 6
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.
Embodiment 1: the synthesis (R of the boric acid ester of quinacridone derivative shown in formula I
1for 2-octyl group-dodecyl) synthesis of quinacridone derivative boric acid ester
First synthetic compound C-1, structural formula is as follows:
The compd A-1 of following structure, B-1 is related in building-up process:
First containing in highly basic, phase-transfer catalyst, toluene system, quinacridone and R-Br are obtained by reacting A-1.Compd A-1 and bromine are obtained by reacting B-1 under mildly acidic conditions.The concrete preparation process of A-1, B-1 can reference: Applied materials & interfaces, 2010,2,2679.
In 250 milliliters of two-mouth bottles, 500 milligrams of B-1 are added in 80 ml acetic anhydride, add the propane dinitrile of three times of molar equivalents, heated overnight at reflux, boils off diacetyl oxide, and solid is through silica gel column chromatography, sherwood oil: ethyl acetate=2:1 wash-out, obtains C-1, productive rate 25%.Molecular ion peak: 1124.1.
By the reaction equation of quinacridone derivative boric acid ester shown in Compound C-1 preparation formula I be:
Concrete preparation method is: under argon shield; 500 milligrams of Compound C-1,300 milligrams of connection pinacol borates, 35 milligrams of Potassium ethanoates are added to 200 milliliter 1; in 4-dioxane; add 20 milligram 1; two (diphenylphosphine) ferrocene of 1'-] palladium chloride; be heated to 80 DEG C spend the night; be extracted with ethyl acetate after reaction terminates; pressure reducing and steaming ethyl acetate; gained solid silica gel column chromatography; methylene dichloride is eluent, obtains the boric acid ester of quinacridone derivative shown in formula I, productive rate 24%.Molecular ion peak: 1220.4.
1H NMR(400MHz,CDCl
3)δ=9.91(s,2H,ArH),9.45(s,2H,ArH),8.54(d,J=8.44Hz,2H,ArH),8.02(d,J=8.50Hz,2H,ArH),4.76(d,4H,CH
2),3.29(m,2H,CH),1.98-1.11(m,64H,CH
2),0.98-0.77(m,36H,CH
3)
Embodiment 2: the synthesis (R of the boric acid ester of quinacridone derivative shown in formula I
1for decyl)
First synthetic compound A-2, B-2, structural formula is as follows:
First, in 500 milliliters of two-mouth bottles, add 1 gram of quinacridone, 2.1 grams of Tetrabutyl amonium bromides; 0.8 gram of sodium hydride, makes solvent with toluene, argon shield; be warming up to 120 DEG C of reaction 2h; drip 1-bromo-decane, reaction cools after spending the night, and is spin-dried for toluene; solid silica gel column chromatography; with sherwood oil: methylene dichloride=2: 1 wash-out, obtain shallow green powder and be A-2, productive rate 30%.Molecular ion peak: 592.6.
In 250 milliliters of two-mouth bottles, add 400 milligrams of A-2,0.8 milligram of Potassium ethanoate, 100 milliliters of acetic acid, be heated to 80 DEG C, inject 0.05 milliliter of Br
2with chloroform extraction after reaction 4h, silica gel column chromatography, sherwood oil: ethyl acetate=10:1 wash-out, obtaining safran solid is B-2, productive rate 70%.Molecular ion peak: 750.6.
In 500 milliliters of two-mouth bottles, 800 milligrams of B-2 are added in 120 ml acetic anhydride, add the propane dinitrile of three times of molar equivalents, heated overnight at reflux, boils off diacetyl oxide, and solid is through silica gel column chromatography, sherwood oil: ethyl acetate=1:1 wash-out, obtains C-2, productive rate 20%.Molecular ion peak: 846.81.C-2 structural formula is as follows:
With Compound C-2 for reactant, the reaction equation preparing boric acid ester is:
Concrete preparation method is: under argon shield; 300 milligrams of Compound C-2,180 milligrams of connection pinacol borates, 12 milligrams of Potassium ethanoates are added to 200 milliliter 1; in 4-dioxane; add 21 milligram 1; two (diphenylphosphine) ferrocene of 1'-] palladium chloride; be heated to 80 DEG C spend the night; be extracted with ethyl acetate after reaction terminates; pressure reducing and steaming ethyl acetate; gained solid silica gel column chromatography; methylene dichloride is eluent, obtains the boric acid ester of quinacridone derivative shown in formula I, productive rate 22%.Molecular ion peak: 940.6.
1H NMR(400MHz,CDCl
3)δ=8.90(s,2H,ArH),8.63(d,J=8.30Hz,2H,ArH),8.01(d,J=8.25Hz,2H,ArH),7.52(s,2H,ArH),4.03(t,4H,CH
2),1.78-1.55(m,35H,CH
2),1.23-0.90(m,30H,CH
3)
Embodiment 3: compound (R shown in preparation formula II
1for 2-octyl group-dodecyl, Ar is preferably Ar-1)
Relate to the preparation of Compound D, E, F in preparation Ar-1 process, structural formula is as follows:
The preparation of Compound D, E, F:
Under strongly alkaline conditions, cyano thiophene and Succinic acid dimethylester are obtained by reacting Compound D;
In the DMF solution containing weak base, phase-transfer catalyst, Compound D and the bromo-2-octyl group-dodecane of 1-are obtained by reacting E.In trichloromethane, add compd E and N-bromo-succinimide, obtain F; Concrete preparation process reference: Macromolecules, 2010,43,821.
As follows by the reaction equation of compound shown in quinacridone derivative boric acid ester preparation formula II:
Concrete preparation process is: under argon shield condition; in round-bottomed flask, add 54 milligrams of embodiments 1 prepare the boric acid ester of compound quinacridone derivative shown in gained formula I, 90 milligrams of compound F 17-hydroxy-corticosterones, 2 milliliters of solution of potassium carbonate (2mol/L), 3.3 milligrams of tetra-triphenylphosphine palladiums; 8 milliliters are heavily steamed toluene; removing oxygen post-heating to 110 DEG C reaction 20h; pressure reducing and steaming toluene; solid silica gel column chromatography, sherwood oil: methylene dichloride=1:1 wash-out, obtaining violet solid is product.Productive rate 65%.Molecular ion peak: 2688.4.
1H NMR(400MHz,CDCl
3)δ=9.55（s,2H,ArH）,9.08(s,2H,ArH),8.94(s,2H,ArH),8.85(s,2H,ArH),8.32(d,2H,ArH),7.98(d,2H,ArH),7.68(d,4H,ArH),7.40(s,2H,ArH),4.67(m,4H,CH
2),4.33(m,8H,CH
2),2.56(m,2H,CH),1.99(m,4H,CH),1.43-1.33(m,190H,CH
2),0.95-0.82(m,36H,CH
3)。
This reaction also can use salt of wormwood, sodium carbonate as weak base, and tetrahydrofuran (THF) or DMF are as solvent, and catalyzer can select dichloro two triphenylphosphine palladium, 1,1'-two (diphenylphosphine) ferrocene] palladium chloride.Consider reaction needed comparatively high temps, therefore preferably solvent made by toluene, the four triphenyl phosphorus palladiums that catalyst choice is conventional, the reaction times is too short, and not exclusively, overlong time then side reaction increases in reaction, therefore the preferred reaction times is 20 hours.
Embodiment 4: polymkeric substance shown in preparation formula III
Polyreaction equation is:
Formula III
Before polymkeric substance described in preparation formula III, need prepare compound G and H, syntheti c route is as follows:
Bromo-5,6-bis-octyloxy benzo [C] [1,2, the 5] thiadiazoles of raw material 4,7-bis-can be bought and obtain.
The preparation of compound G: in 200 milliliters of two-mouth bottles, add 600 milligram 4,7-bis-bromo-5,6-bis-octyloxy benzo [C] [1,2,5] thiadiazoles, 895 milligrams of 2-tributyl thiophene stannanes, 50 milligram of two triphenylphosphine palladium, heavily steam toluene, vacuumize deoxygenation, then be filled with argon gas, be warming up to 110 DEG C of reactions and spend the night.Be cooled to room temperature after reaction terminates, add 10mL potassium fluoride solution and stir 2h, be spin-dried for toluene, with dichloromethane extraction, be spin-dried for rear silica gel column chromatography, with sherwood oil: methylene dichloride=3: 1 wash-out.Obtain yellow greenish powder and be product.Molecular ion peak: 556.7.
The preparation of compound H: in 200 milliliters of single port bottles, adds 600 milligrams of compound G, 426 milligrams of N-bromo-succinimides, 80 milliliters of trichloromethanes, lucifuge reaction 20h under room temperature.After reaction terminates, be spin-dried for trichloromethane, with silica gel column chromatography, sherwood oil wash-out, obtains orange solids and is product H.Molecular ion peak: 714.2.
1HNMR（400MHz,CDCl
3）δ=8.24(d,2H,ArH),7.04(d,2H,ArH),4.01(d,4H,OCH
2),1.85(m,4H,CH
2),1.23(m,20H,CH
2),0.82(m,6H,CH
3)。
Polymkeric substance (R, R shown in preparation formula III
1be 2-octyl group-dodecyl) be specially: in polymerization bottle, add 130 milligrams of embodiments 1 prepare compound 2 shown in gained formula I, 9-hypoboric acid pinacol ester-5, 12-dicyano replaces quinacridone, 143 milligrams of compound Hs, 2 milliliters of solution of potassium carbonate (2mol/L), an Aliquat336, 8 milligrams of tetra-triphenylphosphine palladiums and 4 milliliters of toluene solvants, vacuumize deoxygenation, be filled with argon gas, solution is heated to 110 DEG C, Suzuki polyreaction 72h, after cooling, 50mg phenylo boric acid is added under argon shield, be heated to 110 DEG C of Suzuki linked reaction 6h, again be cooled to room temperature, 50mg bromobenzene is added under argon shield, be heated to 110 DEG C, Suzuki coupling end capping spends the night.Reaction terminates to purify to reaction afterwards: dropwise joined in methyl alcohol by reaction soln, separate out black floss, after filtering, solid filter paper is coated, put into apparatus,Soxhlet's, use methyl alcohol, acetone, normal hexane, dichloromethane extraction 24h successively, collect n-hexane extract, be again deposited in methyl alcohol, filtration final vacuum is dry, and black powder is product.GPC (PEG): Mn=14,475g/mol; Mw=23,539g/mol; PDI=1.6, the polymerization degree is 10.
Embodiment 5: the organic solar batteries preparing structure shown in Fig. 1
Device architecture is: glass/ITO/PEDOT:PSS/ active coating/Al.With the glass with indium tin oxide (ITO) conductive layer for substrate, ITO surface spin coating a layer thickness is 20nm poly-3,4-Ethylenedioxy Thiophene (PEDOT) and poly styrene sulfonate (PSS) are as decorative layer, the photoactive layer (polymkeric substance shown in the formula III that the embodiment 4 being 1:4 by mass ratio provides and PCBM mixing form) that spin coating thickness is 80nm, then on photoactive layer, evaporation thickness is lithium fluoride and the metallic aluminium of 4nm, 10nm successively.
The I-V curve of gained organic solar batteries as shown in Figure 2, wherein, perpendicular to transverse axis and the straight line J corresponding to the intersection point of curve being parallel to transverse axis
scand V
oc.This polymkeric substance has larger open circuit voltage (V as can be seen from Figure 2
oC=0.8V).By optimizing filming condition, can short-circuit current be improved, thus obtain higher energy conversion efficiency.
Embodiment 6: the organic field effect tube preparing structure shown in Fig. 3
The structure of organic field effect tube is: Si/SiO
2/ OTS/ organic semiconductor layer/source electrode (S) and drain electrode (D).Highly doped silicon is as substrate, and thickness is the SiO of 300nm
2as insulation layer, modify SiO by the unimolecular layer of octadecyl trichlorosilane alkane (OTS)
2layer, the embodiment 4 being 80nm by thickness is prepared polymkeric substance shown in gained formula III and is spin-coated in octadecyl trichlorosilane alkane unimolecular layer, and then on organic semiconductor layer, evaporation thickness is source electrode (S) and the drain electrode (D) of 60nm.
Because small molecules containing quinacridone unit provided by the invention or polymkeric substance in atmosphere can stable existences, therefore all operations (except annealing) can carry out in atmosphere.The present invention uses keithley 4200 semiconductor test system to test transition curve and the curve of output of OFET in atmosphere, and as shown in Figure 4, left figure A represents that source-drain current is with grid voltage change curve; B represents that source-drain current square root is with grid voltage change curve; .Because this quasi-molecule is solvable in conventional organic solvent, good film-forming property, hole mobility is higher, can reach 0.2cm
2/ (Vs).
Embodiment 3 prepares compound shown in gained formula II as the performance test results of organic field effect tube and above-described embodiment 5 and 6 without substantive difference, repeats no more herein.
Claims (20)
1. compound shown in formula I,
In described formula I, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one;
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR'; Wherein, R' is C
1-C
20alkyl or NH
2.
2. prepare the method for compound described in claim 1 for one kind, comprise the steps: under catalyzer and weak base existent condition, in inert atmosphere, compound shown in formula C is mixed with connection pinacol borate and carries out Suzuki linked reaction, react complete and obtain compound shown in described formula I;
In described formula C, R
1and R
2definition identical with claim 1.
3. method according to claim 2, is characterized in that: described catalyzer is selected from least one in 1,1'-[two (diphenylphosphine) ferrocene] palladium chloride, dichloro two triphenylphosphine palladium and four triphenyl phosphorus palladiums;
Described weak base is selected from least one in Potassium ethanoate, salt of wormwood and sodium carbonate;
Described reaction is carried out in a solvent; Described solvent is selected from least one of Isosorbide-5-Nitrae-dioxane, tetrahydrofuran (THF) and DMF;
The mass ratio of compound shown in described pinacol borate, catalyzer, weak base and formula C is 0.3-0.8:0.04-0.08:0.03-0.06:1;
In described Suzuki linked reaction step, temperature is 60-100 DEG C, and the time is 10-24 hour;
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere.
4. method according to claim 3, is characterized in that: the mass ratio of compound shown in described pinacol borate, catalyzer, weak base and formula C is 0.6:0.07:0.04:1;
In described Suzuki linked reaction step, temperature is 80 DEG C, and the time is 18 hours.
5. compound described in formula II,
In described formula II, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one;
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR'; Wherein, R' is C
1-C
20alkyl or NH
2;
Ar is selected from
in at least one;
Described R is H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one
X is S, O or N;
M and n is the integer of 0-5.
6. prepare the method for compound shown in formula II described in claim 5 for one kind, comprise the steps: under inert atmosphere and catalyzer existent condition, Suzuki linked reaction is carried out in the mixing of compound shown in compound and Br-Ar described in weak alkaline aqueous solution, claim 1, reacts complete and obtain compound shown in described formula II;
In described Br-Ar, the definition of Ar is identical with claim 5.
7. method according to claim 6, is characterized in that: described catalyzer is selected from least one in tetra-triphenylphosphine palladium, 1,1'-[two (diphenylphosphine) ferrocene] palladium chloride and dichloro two triphenylphosphine palladium;
Described weak base is selected from least one in salt of wormwood, potassiumphosphate, Potassium ethanoate and sodium-acetate;
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere;
The concentration of the aqueous solution of described weak base is 0.5-3.0mol/L;
Described in described catalyzer, weak base, bromide Br-Ar and claim 1, the mass ratio of compound is 0.05-0.1:0.05-0.09:1.5-2.5:1;
In described Suzuki linked reaction step, temperature is 70-120 DEG C, and the time is 10-24 hour;
Described Suzuki linked reaction is carried out in a solvent; Described solvent is selected from least one in toluene, tetrahydrofuran (THF) and DMF.
8. method according to claim 7, is characterized in that: described Br-Ar is
The concentration of the aqueous solution of described weak base is 2mol/L
Described in described catalyzer, weak base, bromide Br-Ar and claim 1, the mass ratio of compound is 0.06:0.07:1.8:1;
In described Suzuki linked reaction step, temperature is 110 DEG C, and the time is 20 hours.
9. alternating copolymer shown in formula III,
In described formula III, R
1for H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one;
R
2for-CN ,-COOH ,-COOR', NH
2, NO
2, HCO-or-COR'; R' is C
1-C
20alkyl or NH
2;
The integer that n ' is 7-50;
Ar ＇ is:
Described R is H, halogen, C
1-C
20alkyl, halogen substiuted C
1-C
20alkyl, C
1-C
20alkoxyl group, halogen substiuted C
1-C
20alkoxyl group, sulfonic group, the sulfonic group of halogen substiuted, C
1-C
20aromatic base, containing substituent C
1-C
20aromatic base, C
1-C
20aromatic condensed ring base or containing substituent C
1-C
20aromatic condensed ring base;
Described containing substituent C
1-C
20aromatic base and containing substituent C
1-C
20aromatic condensed ring base in, substituting group is selected from halogen, C
1-C
20alkyl and C
1-C
20alkoxyl group at least one;
X is S, O or N;
M and n is the integer of 0-5, and m is not 0.
10. prepare the method for polymkeric substance shown in formula III described in claim 9 for one kind, comprise the steps: under inert atmosphere and catalyzer existent condition, after Suzuki polyreaction is carried out in compound shown in formula I described in the aqueous solution of weak base, claim 1, two bromine substituent Br-Ar'-Br, phase-transfer catalyst mixing, after cooling and phenylo boric acid or 2-boric acid thiophene carry out Suzuki linked reaction after carry out Suzuki coupling end-blocking with bromobenzene or 2-bromo thiophene again, react complete and obtain polymkeric substance shown in described formula III;
In described Br-Ar'-Br, the definition of Ar' is identical with claim 9.
11. methods according to claim 10, is characterized in that: described catalyzer is selected from least one in tetra-triphenylphosphine palladium, 1,1'-[two (diphenylphosphine) ferrocene] palladium chloride and dichloro two triphenylphosphine palladium;
Described weak base is selected from least one in salt of wormwood, potassiumphosphate, Potassium ethanoate and sodium-acetate;
Described phase-transfer catalyst is methyl tricapryl ammonium chloride;
Described inert atmosphere is argon gas atmosphere or nitrogen atmosphere;
The concentration of the aqueous solution of described weak base is 0.5-3mol/L;
Described in described catalyzer, weak base, Aliquat336, two bromine substituent Br-Ar'-Br and claim 1, the mass ratio of compound is 0.05-0.1:0.05-0.09:0.001-0.01:0.8-1.6:1;
In described Suzuki polymerization procedure, temperature is 80-130 DEG C, and the time is 36-78 hour;
Described Suzuki polyreaction is carried out in a solvent; Described solvent is selected from least one in toluene, tetrahydrofuran (THF) and DMF;
Described in described phenylo boric acid or 2-boric acid thiophene, bromobenzene or 2-bromo thiophene and claim 1, the mass ratio of compound is 0.002-0.05:0.002-0.05:1;
In described Suzuki coupling end capping step, temperature is 80-130 DEG C, and the time is 5-10 hour.
12. methods according to claim 11, is characterized in that: described couple of bromine substituent Br-Ar'-Br is
The concentration of the aqueous solution of described weak base is 2mol/L;
Described in described catalyzer, weak base, Aliquat336, two bromine substituent Br-Ar'-Br and claim 1, the mass ratio of compound is 0.06:0.07:0.005:1.1:1;
In described Suzuki polymerization procedure, temperature is 110 DEG C, and the time is 72 hours;
Described in described phenylo boric acid or 2-boric acid thiophene, bromobenzene or 2-bromo thiophene and claim 1, the mass ratio of compound is for being preferably 0.004:0.004:1;
In described Suzuki coupling end capping step, temperature is 110 DEG C, and the time is 6 hours.
13. organic solar batteries containing polymkeric substance described in compound or 9 described in claim 1 or 5.
14. organic solar batteries according to claim 13, is characterized in that: described in described claim 1 or 5, polymkeric substance described in compound or 9 is the photoactive layer in described organic solar batteries.
15. organic field effect tubes containing polymkeric substance described in compound or 9 described in claim 1 or 5.
16. organic field effect tubes according to claim 15, is characterized in that: described in described claim 1 or 5, polymkeric substance described in compound or 9 is the charge transport layer in described organic field effect tube.
Described in 17. claims 1 or 5, polymkeric substance described in compound or 9 is preparing the application in organic solar batteries.
18. application according to claim 17, is characterized in that: described organic solar batteries of preparing is the photoactive layer preparing described organic solar batteries.
Described in 19. claims 1 or 5, polymkeric substance described in compound or 9 is preparing the application in organic field effect tube.
20. application according to claim 19, is characterized in that: described organic field effect tube of preparing is the charge transport layer preparing organic field effect tube.
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| CN101671428A (en) * | 2008-09-09 | 2010-03-17 | 中国科学院化学研究所 | Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof |
| CN102060854A (en) * | 2010-11-25 | 2011-05-18 | 吉林大学 | Nitrile substituted quinacridone compounds and application thereof in organic solar cell |
| CN102276600A (en) * | 2011-04-22 | 2011-12-14 | 华东理工大学 | Quinacridone derivative and application thereof |
| CN102408547A (en) * | 2011-10-24 | 2012-04-11 | 中国科学院化学研究所 | Benzodifuran conjugated polymer material and preparation method and application thereof |
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| CN101671428A (en) * | 2008-09-09 | 2010-03-17 | 中国科学院化学研究所 | Conjugated polymer based on condensed ring thiophene and diazosulfide as well as preparation method and application thereof |
| CN102060854A (en) * | 2010-11-25 | 2011-05-18 | 吉林大学 | Nitrile substituted quinacridone compounds and application thereof in organic solar cell |
| CN102276600A (en) * | 2011-04-22 | 2011-12-14 | 华东理工大学 | Quinacridone derivative and application thereof |
| CN102408547A (en) * | 2011-10-24 | 2012-04-11 | 中国科学院化学研究所 | Benzodifuran conjugated polymer material and preparation method and application thereof |
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