CN102675349A - Pyrroledione phthalocyanine conjugate derivative and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a pyrroledione phthalocyanine conjugate derivative and a preparation method and application thereof. In the pyrroledione phthalocyanine conjugate derivative indicated in a formula I, R1 is C1-C3 alkyl; R2 is hydrogen or C1-C30 alkyl; X is an O, S or Se atom; M is Zn, Cu, Ni, Al-Cl, Mn, Ru, Fe or Co. The preparation method of the conjugate derivate comprises the following steps that: (1) 4-bromobenzene-1, 2-dicyano and bispinacolatodiboron are reacted under the catalysis of normal butyl lithium to obtain a compound indicated in a formula II; (2) the compound indicated in the formula II and the compound indicated in a formula III are reacted under the effect of an alkaline compound and a catalyst a; and (3) compound indicated in a formula IV and 1,8-diazabicyclo[5.4.0] 11-carbon-7-alkene are reacted under the effect of a catalyst b to obtain the pyrroledione phthalocyanine conjugate derivative. The pyrroledione phthalocyanine conjugate derivative indicated in the formula I can be used as a donor material in an active layer of a solar cell.
Description
Technical field
The present invention relates to a kind of and pyrroledione-phthalocyanine conjugate derivative and preparation method thereof and application.
Background technology
Phthalocyanine is one type of important organic molecule material, and this compounds has good light stability, thermostability and unreactiveness; [Markus K.R.Fischer has a wide range of applications aspect solar cell; J.Am.Chem.Soc.2009,131,8669 – 8676; Alessandro Varotto, J. Am.Chem.Soc.2010,132,2552 – 2554; JeaUk Lee, J.Mater.Chem., 2011,21,17209 – 17218].Yet because the solution processing poor performance of phthalocyanine molecule adopts vacuum-deposited method vapor deposition active coating usually, this has limited the application of phthalein mountain valley with clumps of trees and bamboo verivate to a certain extent.
And pyrroledione (DPP) is common industrial dye; Have strong photoabsorption, wide light abstraction width; The DPP conjugation is coupled at the big electron conjugated compound of formation on the phthalocyanine, and the band gap of compound reduces, and light abstraction width increases; Help compound and absorb the formation exciton that is stimulated after the sunshine, photoelectric current is enlarged markedly.Moreover; The DPP group is connected through the C-C singly-bound with phthalocyanine; The introducing of DPP makes compound that good processing properties arranged, and with inducing in the mutually heterogeneous junction battery of body, forming reasonably with acceptor material of phthalocyanine group to be separated, makes the exciton of formation can separate and be transferred to electrode effectively.So far also not for and the relevant report of pyrroledione conjugation phthalocyanine compound and verivate thereof, therefore provide a kind of new and pyrroledione conjugation phthalocyanine derivates and preparation method thereof to have great importance.
Summary of the invention
The purpose of this invention is to provide a kind of and pyrroledione-phthalocyanine conjugate derivative and preparation method thereof and application.
Provided by the invention and pyrroledione-phthalocyanine conjugate derivative, its structure be suc as formula shown in the I,
Formula I
Among the formula I, R
1Be C
1~ C
30Alkyl; R
2Be hydrogen or C
1~ C
30Alkyl; X is O, S or Se atom; M is Zn, Cu, Ni, Al-Cl, Mn, Ru, Fe or Co.
The present invention also provides shown in the formula I and the preparation method of pyrroledione-phthalocyanine conjugate derivative, comprises the steps:
(1) under the condition of anhydrous and oxygen-free, 4-bromobenzene-1,2-dicyano and duplex tetramethyl ethylene ketone boric acid ester react under the catalysis of n-Butyl Lithium and obtain compound shown in the formula II;
The formula II
(2) under inert atmosphere, compound shown in compound shown in the formula II and the formula III reacts under the effect of basic cpd and catalyzer a and obtains compound shown in the formula IV;
Formula III formula IV
In the formula, R
1Be C
1~ C
30Alkyl; R
2Be hydrogen or C
1~ C
30Alkyl; X is O, S or Se atom;
(3) compound and 1 shown in the formula IV, 8-diazabicylo [5.4.0] 11 carbon-7-alkene react under the effect of catalyzer b and promptly get shown in the formula I and pyrroledione-phthalocyanine conjugate derivative.
Among the above-mentioned preparation method, in the step (1), 4-bromobenzene-1, the molfraction ratio of 2-dicyano, duplex tetramethyl ethylene ketone boric acid ester and n-Butyl Lithium can be 1: (1 ~ 1.3): (1 ~ 1.3) specifically can be 1:1.1:1.1.
Among the above-mentioned preparation method, in the step (1), the solvent of said reaction can be THF; The consumption of said solvent can be: every 1mmol4-bromobenzene-1,2-dicyano need that (the said solvent of 3mL ~ 6mL) is like 5mL.
Among the above-mentioned preparation method, in the step (1), the temperature of said reaction can be-40 ℃ ~-78 ℃, specifically can be-78 ℃, and the time of said reaction can be 1.5 ~ 3h, specifically can be 2h.
Among the above-mentioned preparation method, in the step (2), compound shown in the formula II can be (1 ~ 2) with the molfraction ratio of compound shown in the formula III: 1, specifically can be 2:1 or 1.9:1; Said catalyzer a can be tetrakis triphenylphosphine palladium, [1; Two (diphenylphosphine) ferrocene of 1'-] palladium chloride or palladium; Said catalyzer a can be (0.01 ~ 0.05) with the molfraction ratio of compound shown in the formula II: 1, specifically can be 0.01:1 or 0.02:1.
Among the above-mentioned preparation method, in the step (2), the solvent of said reaction can be toluene, N ' dinethylformamide or acetonitrile; The consumption of said solvent can be: compound shown in every 1mmol formula II needs that (the said solvent of 4mL ~ 6mL) is like 5mL; Said basic cpd can be salt of wormwood, specifically can adopt the form of unsaturated carbonate potassium solution, and used unsaturated carbonate potassium solution is (4 ~ 6) with the volume parts ratio of the solvent of said reaction: 1, like 5:1; The temperature of said reaction can be 100 ℃ ~ 135 ℃, specifically can be 135 ℃, and the time can be 10h ~ 24h, specifically can be 24h; Said inert atmosphere can be nitrogen.
Among the above-mentioned preparation method, in the step (3), said catalyzer b can be zinc chloride or cupric chloride; Compound, 1 shown in the formula IV, 8-diazabicylo [5.4.0] 11 carbon-7-alkene can be 1 with the molfraction ratio of catalyzer b: (1 ~ 1.2): (1.3 ~ 1.6) specifically can be 1:1:1.4 or 1:1:1.5; The solvent of said reaction can be Pentyl alcohol, and the consumption of said solvent can be: compound shown in every 1mmol formula IV needs that (the said solvent of 20mL ~ 35mL) is like 25mL or 26mL; The temperature of said reaction can be 125 ℃ ~ 140 ℃, specifically can be 135 ℃, and the reaction times can be 4.5h ~ 6h, specifically can be 5h.
The present invention also further provides shown in the formula I and the application of pyrroledione-phthalocyanine conjugate derivative in the preparation organic solar batteries; Can prepare phase heterojunction photovoltaic device through the solution spin-coating method, solve the phthalocyanine material and be difficult to the problem of solution processing, and widened the absorption region of molecule, increase photoelectric current and device efficiency.
The present invention has following beneficial effect: provided by the invention and pyrroledione-phthalocyanine conjugate derivative can prepare through simple synthesis step in a large number; Be soluble in common organic solvent; In methylene dichloride, THF or trichloromethane, compare with other phthalocyanine derivates, can prepare the uniform film of high quality through solution methods; The light abstraction width broadening is to the 700nm; Energy gap is narrower, and the formation exciton that is stimulated easily behind the extinction can be used as the donor material in the solar cell active coating.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of compound shown in the formula 5 of embodiment 1 preparation.
Fig. 2 is the hydrogen spectrogram of compound shown in the formula 5 of embodiment 1 preparation.
Fig. 3 is the structural representation of the photovoltaic device of preparation among the embodiment 4.
Fig. 4 is the current-voltage relation curve figure of the photovoltaic device of preparation among the embodiment 4.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The synthetic route of present embodiment is shown below:
(1) under the anhydrous and oxygen-free condition, with 4-bromobenzene-1,2-dicyano (412mg; 2mmol) be dissolved in the 10ml THF (THF), low temperature-78 ℃ stirring, adding concentration then is the n-Butyl Lithium (1.0ml of 2.2M; 2.2mmol); Low-temp reaction add after 0.5 hour duplex tetramethyl ethylene ketone boric acid ester (280mg, 2.2mmol) ,-78 ℃ of down reactions 2 hours; Reaction finishes after washing, and extraction obtains compound shown in the formula II (340mg, 1.34mmol, productive rate 67%) after the chromatographic silica gel post separates.
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR (400MHz, CHCl
3, δ (ppm)): 8.21 (d, 2H), 7.87 (s, 2H), 7.82 (d, 2H), 1.24 (s, 12H); The structure of confirming product is correct.
(2) under nitrogen protection, with the 2-cyano thiophene (3.27g, 30mmol) and succinate (1.46g; 10mmol) successively join sodium tert-butoxide (3.36g; In 2-methyl amyl alcohol (25ml) solution 30mmol), 110 ℃ of refluxed stirred 2 hours, and adding acetic acid cancellation after-filtration water and methyl alcohol are washed and obtained compound (2.29g shown in the product formula 1; Productive rate 63%), directly carry out next step reaction without purifying.
(3) under nitrogen protection, with compound shown in the formula 1 (1.3g, 4.3mmol), anhydrous K
2CO
3(2.4g 17mmol) is dissolved among the 25ml DMF, is heated to 145 ℃, and (3.86g 20mmol), reacted 12 hours to add 2-ethylhexyl bromine; Reaction is poured reaction soln in a large amount of cold water into after finishing, and filters, and residue water and methyl alcohol repeatedly clean, and silicagel column is crossed in dry back, obtains compound shown in the formula 2 (1.6g, 2.4mmol, productive rate 59%).
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR (400MHz, CHCl
3, δ (ppm)): 8.11 (d, 2H), 8.05 (d, 2H), 7.52 (m, 2H), 4.01 (d, 4H) 2.10 (m, 2H), 1.2-1.5 (m, and 16H) 0.88 (m, 12H); MALDI-TOF MS:m/z=524.3 (M
+), confirm that the structure of product is correct.
(4) under the room temperature condition, (1.6g 2.4mmol) joins in the chloroformic solution, and lucifuge is reacted, and (384mg, 2.1mmol) reaction obtained compound shown in the formula 3 (472mg, 0.9mmol, productive rate 38%) after 2 hours to add NBS then with compound shown in the formula 2.
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR (400MHz, CHCl
3, δ (ppm)): 8.11 (d, 1H), 8.05 (d, 1H), 7.78 (m, 1H), 7.52 (m, 1H), 7.26 (d, 1H), 4.01 (d, 4H), 2.10 (m, 2H), 1.2-1.5 (m, 16H), 0.88 (m, 12H); MALDI-TOFMS:m/z=604.2 (M
+), confirm that the structure of product is correct.
(5) under nitrogen protection, (310mg, 1.8mmol) (472mg 0.9mmol) mixes in the adding toluene (10ml), adds the saturated K of 2ml with compound shown in the formula 3 with compound shown in the formula II
2CO
3Solution, (20mg 0.018mmol) 135 ℃ of refluxed reactions 24 hours, obtains compound shown in the formula 4 (468mg, 0.72mmol, productive rate 80%) through the silicagel column purification to add catalyzer four (triphenyl phosphorus) palladium.
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR (400MHz, CHCl
3, δ (ppm)): 8.24 (d, 1H), 8.11 (d, 1H), 8.05 (m, 3H), 7.91 (d, 1H), 7.78 (d, 1H), 7.52 (m, 1H), 4.01 (d, 4H), 2.10 (m, 2H), 1.2-1.5 (m, 16H), 0.88 (m, 12H); MALDI-TOF MS:m/z=650.3 (M
+), confirm that the structure of product is correct.
(6) under nitrogen protection, with compound shown in the formula 4 (468mg, 0.72mmol), 1,8-diazabicylo [5.4.0] 11 carbon-7-alkene DBU (110mg, 0.72mmol) and ZnCl
2(136mg, 1mmol) refluxing and stirring obtained the also pyrroledione-zinc phthalocyanine conjugate derivative (270mg, 0.1mmol, productive rate 54%) shown in the formula 5 in 5 hours in Pentyl alcohol (18ml).
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3，δ(ppm)):9.17(m,4H),8.90(d,4H),8.24(m,4H),7.65(d,4H),7.50(s,4H),7.42(d,4H),7.26(d,4H),7.22(d,4H),4.01(m,16H),1.84(m,8H),1.25-1.55(m,64H),0.88(m,48H);MALDI-TOF?MS:m/z=2729.1(M+)；
The hydrogen spectrogram of product is as shown in Figure 2, and figure is as shown in Figure 1 for its ultraviolet-visible absorption spectroscopy.
Identical among concrete synthesis step and the embodiment 1, difference is: in step (6) with ZnCl
2Be replaced by CuCl
2, obtain the also pyrroledione-copper phthalocyanine conjugate derivative shown in the formula 6.
MALDI-TOF?MS：m/z=2728.3(M
+)。
The synthetic route of present embodiment is shown below:
(1) (800mg 1.2mmol), joins anhydrous CH with compound shown in the formula that obtains among the embodiment 12
2Cl
2(15ml), (160mg, 1.2mmol) 30 minutes postcooling to 0 of stirring at room ℃ add AlCl afterwards to add the hexyl acyl chlorides
3(215mg, 1.6mmol), stirring at room was reacted with the frozen water cancellation after 2 hours; Filter extraction, utilize silicagel column purification acquisition formula 7 to show compound (680mg, 1.1mmol, productive rate 90%);
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3,δ(ppm)):8.27(d,1H),8.11(d,1H),8.05(d,2H),7.52(d,1H),4.01(d,4H),3.30(d,2H),2.10(m,2H),1.2-1.5(m,22H),0.88(m,15H);MALDI-TOFMS:m/z=622.3(M
+)。
(2) under nitrogen protection, with LiAlH
4(300mg, 8mmol) and AlCl
3(400mg 3mmol) joins in the anhydrous diethyl ether, under 0 ℃, then formula 7 is shown compound (680mg; 1.1mmol) join in the reaction soln, room temperature reaction is 3 hours afterwards, and reaction is poured reaction soln in the cold water into after finishing; Extraction; Cross the silicagel column purification and obtain compound shown in the formula 8 (600mg, 1mmol, productive rate 88%);
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3，δ(ppm)):8.11(d,1H),8.05(d,1H),7.81(d,1H),7.52(m,1H),7.18(d,1H),4.01(d,4H),2.77(t,2H),2.10(m,2H),1.2-1.5(m,22H),0.88(m,15H);MALDI-TOF?MS:m/z=608.4(M
+)。
(3) under the room temperature condition, (600mg 1mmol) joins in the chloroformic solution, the lucifuge reaction with compound shown in the formula 8; (84mg 2.1mmol), reacts after washing extraction in 2 hours to add NBS then; Cross silicagel column and obtain compound shown in the formula 9 (460mg, 0.67mmol, productive rate 67%);
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3，δ(ppm)):7.81(d,1H),7.78(d,1H),7.32(d,1H),7.18(d,1H),4.01(d,4H),2.77(t,2H),2.10(m,2H),1.2-1.5(m,16H),0.88(m,12H);MALDI-TOFMS:m/z=688.3(M
+)。
(4) (460mg, 0.67mmol) (230mg 1.3mmol) is mixed to join in the toluene solution, adds the saturated K of 2ml afterwards with compound shown in the formula II with compound shown in the formula 9 under nitrogen protection
2CO
3Solution, and catalyzer four (triphenyl phosphorus) palladium (23mg, 0.02mmol) at 25mg, 135 ℃ of refluxed reactions 24 hours, reaction finished the after washing extraction, and purifying through the chromatographic silica gel post obtains compound shown in the formula 10 (367mg, 0.5mmol, productive rate 73%);
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3，δ(ppm)):7.24(d,1H),8.05(m,2H),7.91(s,1H),7.88(d,1H),7.81(d,1H),7.18(d,1H),4.01(d,4H),2.77(t,2H),2.10(m,2H),1.2-1.5(m,16H),0.88(m,12H);MALDI-TOF?MS:m/z=734.4(M
+)。
(5) under nitrogen protection, with compound shown in the formula 10 (367mg, 0.5mmol), DBU (76mg, 0.5mmol) and ZnCl
2(100mg, 0.75mmol) refluxing and stirring obtained shown in the formula 11 in 5 hours and pyrroledione-zinc phthalocyanine derivates (130mg, 0.04mmol, productive rate 34%) in Pentyl alcohol (13ml);
The nuclear-magnetism structural characterization data of this product are following:
1H-NMR(400MHz，CHCl
3，δ(ppm)):9.17(m,4H),8.90(d,4H),8.24(m,4H),7.65(d,4H),7.50(s,4H),7.42(d,4H),7.26(d,4H),7.22(d,4H),4.01(m,18H),1.20-1.55(m,120H),0.88(m,60H);MALDI-TOF?MS:m/z=3065.2(M+)。
The ultraviolet-visible absorption spectroscopy of the phthalocyanine derivates of embodiment 1 preparation is as shown in Figure 1; Can find out from this absorption spectrum; This compound has wide absorption peak in the visible region; This improves its photoabsorption for solar cell, and then improves photoelectric current and have very great help, and can be used to prepare the organic photovoltaic battery of solution processing.
Shown in the formula 5 of 1mg and [6,6]-phenyl-C61 methyl-butyrate (PC of pyrroledione-zinc phthalocyanine conjugate derivative and 1mg
61BM) mix; Add the ultra dried chloroform solvent dissolving of 100 microlitres; Mixed at room temperature stirred 4 hours, through the spin coating mode through gathering the film of preparing about 100nm on the conductive glass that (3, the 4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS) modifies; Be respectively the calcium of 20nm and the aluminium electrode of 80nm through vacuum-deposited mode vapor deposition thickness then, the preparation area is the photovoltaic cell of 2mm*2mm.
Structural representation such as Fig. 3 of the device of this embodiment preparation.
The photovoltaic performance of this device shows as: (AM 1.5,100mw/cm at simulated solar irradiation
2) shine down, producing photoelectricity and transform, the current-voltage curve of being tested is as shown in Figure 4, short-circuit current=5.69mA/cm
2, open circuit voltage=0.76V, packing factor=0.38, efficiency of conversion=1.63%.
Claims (10)
1. shown in the formula I and pyrroledione-phthalocyanine conjugate derivative,
Among the formula I, R
1Be C
1~ C
30Alkyl; R
2Be hydrogen or C
1~ C
30Alkyl; X is O, S or Se atom; M is Zn, Cu, Ni, Al-Cl, Mn, Ru, Fe or Co.
2. shown in the formula I and the preparation method of pyrroledione-phthalocyanine conjugate derivative, comprise the steps:
(1) under the condition of anhydrous and oxygen-free, 4-bromobenzene-1,2-dicyano and duplex tetramethyl ethylene ketone boric acid ester react under the catalysis of n-Butyl Lithium and obtain compound shown in the formula II;
The formula II
(2) under inert atmosphere, compound shown in compound shown in the formula II and the formula III reacts under the effect of basic cpd and catalyzer a and obtains compound shown in the formula formula IV;
Formula III formula IV
In the formula, R
1Be C
1~ C
30Alkyl; R
2Be hydrogen or C
1~ C
30Alkyl; X is O, S or Se atom;
(3) compound and 1 shown in the formula IV, 8-diazabicylo [5.4.0] 11 carbon-7-alkene react under the effect of catalyzer b and promptly get shown in the formula I and pyrroledione-phthalocyanine conjugate derivative.
3. preparation method according to claim 2 is characterized in that: in the step (1), and 4-bromobenzene-1, the molfraction ratio of 2-dicyano, duplex tetramethyl ethylene ketone boric acid ester and n-Butyl Lithium is 1: (1 ~ 1.3): (1 ~ 1.3).
4. according to claim 2 or 3 described preparing methods, it is characterized in that: in the step (1), the solvent of said reaction is a THF; The consumption of said solvent is: every 1mmol4-bromobenzene-1,2-dicyano need (the said solvent of 3mL ~ 6mL).
5. according to arbitrary described preparation method among the claim 2-4, it is characterized in that: in the step (1), the temperature of said reaction is-40 ℃ ~-78 ℃, and the time is 1.5h ~ 3h.
6. according to arbitrary described preparation method among the claim 2-5, it is characterized in that: in the step (2), compound shown in the formula II is (1 ~ 1.5) with the molfraction ratio of compound shown in the formula III: 1; Said catalyzer a is tetrakis triphenylphosphine palladium, [1, two (diphenylphosphine) ferrocene of 1'-] palladium chloride or palladium, and said catalyzer a is (0.01 ~ 0.05) with the molfraction ratio of compound shown in the formula II: 1.
7. according to arbitrary described preparation method among the claim 2-6, it is characterized in that: in the step (2), the solvent of said reaction is toluene, N ' dinethylformamide or acetonitrile; The consumption of said solvent is: compound shown in every 1mmol formula II needs (the said solvent of 4mL ~ 6mL); Said basic cpd is a salt of wormwood; The temperature of said reaction is 100 ℃ ~ 135 ℃, and the time is 10h ~ 24h.
8. according to arbitrary described preparation method among the claim 2-7, it is characterized in that: in the step (3), said catalyzer b is zinc chloride or cupric chloride; Compound, 1 shown in the formula IV, 8-diazabicylo [5.4.0] 11 carbon-7-alkene is 1 with the molfraction ratio of catalyzer b: (1 ~ 1.2): (1.3 ~ 1.6); The solvent of said reaction is a Pentyl alcohol, and the consumption of said solvent is: compound shown in every 1mmol formula IV needs (the said solvent of 20mL ~ 35mL); The temperature of said reaction is 125 ℃ ~ 140 ℃, and the time is 4.5 ~ 6h.
9. the also application of pyrroledione-phthalocyanine conjugate derivative in the preparation organic solar batteries shown in the formula I.
10. organic solar batteries is characterized in that: the active coating of said organic solar batteries comprises shown in the formula I and pyrroledione-phthalocyanine conjugate derivative.
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| CN108409976A (en) * | 2018-01-19 | 2018-08-17 | 北京化工大学 | The topological organic polymer of solubility based on full conjugate rigid structure and quasi- phthalocyanine activated centre and preparation |
| CN110183452A (en) * | 2019-05-16 | 2019-08-30 | 中山大学 | A kind of perfluoro butyl substituted compound and its preparation method and application |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108409976A (en) * | 2018-01-19 | 2018-08-17 | 北京化工大学 | The topological organic polymer of solubility based on full conjugate rigid structure and quasi- phthalocyanine activated centre and preparation |
| CN110183452A (en) * | 2019-05-16 | 2019-08-30 | 中山大学 | A kind of perfluoro butyl substituted compound and its preparation method and application |
| CN110183452B (en) * | 2019-05-16 | 2021-06-01 | 中山大学 | Perfluorobutyl substituted compound and preparation method and application thereof |
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