CN105238092B - A kind of organic dye sensitized dose of BODIPY classes of 2,6 substitutions and preparation method thereof - Google Patents
A kind of organic dye sensitized dose of BODIPY classes of 2,6 substitutions and preparation method thereof Download PDFInfo
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- QLOUQHQDDYJWRM-UHFFFAOYSA-N CCCCCCCC[n]1c(cc(cc2)Br)c2c2ccccc12 Chemical compound CCCCCCCC[n]1c(cc(cc2)Br)c2c2ccccc12 QLOUQHQDDYJWRM-UHFFFAOYSA-N 0.000 description 1
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- Y02E10/542—Dye sensitized solar cells
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Abstract
The present invention relates to a kind of 2,6 organic dye sensitized dose of BODIPY classes of substitution and preparation method thereof.This organic dye sensitized dose is organic photovoltaic material that a class has D π A structures, and the BODIPY cores with meso substitution be π bridge skeletons, replaces to electrophilic unit respectively at the 2 of BODIPY cores, 6.The invention also discloses the preparation method of above-mentioned dye sensitizing agent, it is initial reaction raw materials with 2,4 dimethyl pyrroles, by a series of simple synthetic reactions, dye molecule is obtained finally by classical Suzuki couplings, Knoevenagel condensation reactions, general structure is shown in I.Such dye sensitizing agent synthetic method is simple, it is easy to control, yield is high, with general applicability.It is applied to the preparation of DSSC, the DSSC material of fill factor, curve factor high and preferable photoelectric transformation efficiency can be obtained.
Description
Technical field：
The present invention relates to DSSC Material Field, more particularly to 2,6- BODIPY class of substitution of one kind
Organic dye sensitized dose.
Background technology：
From Switzerland in 1991Group is first using bipyridyl ruthenium as dyestuff and nanoporous TiO2Film preparation
Since DSSC (DSSCs), dye sensitized nano crystal TiO2Solar cell just relies on low preparation cost
Photoelectric transformation efficiency higher carrys out the study hotspot in solar energy photoelectric conversion field as recent two decades.Light-sensitive coloring agent is mainly wrapped
Metal-containing complex and pure organic dye.At present, the metal complex based on [Ru(bpy)2(dppzi) is because of its good stability
Energy conversion efficiency higher, has obtained extensively and in-depth study.But, there is such as resource-constrained, price and hold high in ruthenium dye
The inferior position such as expensive, which has limited its application.Compared with ruthenium dye, pure organic dye is because of its low raw-material cost, structure design spirit
The advantages of living, be easily-synthesized, being easily purified, has become the popular direction of current DSSCs researchs.
Fluorine boron complexing two pyrroles (BODIPY) derivative be the good light-sensitive coloring agent of a class, with good stability, can
Good, the high molar extinction coefficient (1 × 10 of modified5M-1·cm-1) and oxidizing potential higher, it is applied to the dye sensitization sun
Can the existing document report of battery.The spectral absorption relative narrower of BODIPY, but its good modifiability can overcome this
Shortcoming, realizes the red shift of spectral absorption and widens, and is conducive to improving the Jsc of battery, has shown good application prospect.Carbazole
Derivative is the another kind of compound with good photoelectric property.It has strong spectral absorption and emission characteristic, sky very high
Cave transmittability and band gap wider, are widely used in field of photovoltaic materials.In view of the photo electric that two class materials are protruded
Matter, therefore, BODIPY is combined with carbazole compound, it is applied to DSSC and causes our grind
Study carefully interest.
Present invention design has synthesized the new D- π-A dyestuffs that class BODIPY 2,6- is replaced to, receptor unit respectively
Sensitizer, and synthetic method to such dyestuff is optimized, and improves such BODIPY Dyestuff synthesis yield, is effectively improved
The photovoltaic performance of such BODIPY dyestuff.
The content of the invention：
It is an object of the invention to provide 2,6- organic dye sensitized dose of BODIPY class of substitution of one kind, it has novelty
Molecular structure, there are relatively low edge energy, spectral absorption scope wide
It is a further object to provide the preparation method of such dye sensitizing agent, the method reaction condition is easy to control
System, product purification is simple, and yield is higher, and with universality.
To achieve the above object, the present invention uses following technical scheme：
2,6- organic dye sensitized dose of BODIPY class of substitution of one kind, the chemical constitution with formula I：
In formula I, D is donor monomer, is the one kind in following construction unit：
Wherein, R1It is H or alkyl or alkoxy, n is 5；
A is receptor unit, is the one kind in following construction unit：
2,6- preparation method of organic dye sensitized dose of the BODIPY classes of substitution of one kind, comprises the following steps：
(1) be there is into condensation reaction in 2,4- dimethyl pyrroles and acyl chlorides, then complex reaction is carried out with BFEE, made
Intermediate 1 is obtained, its structure is：
(2) intermediate 1 obtains intermediate 2 by dimension David Smail formylation reaction, and its structure is：
(3) intermediate 2 is obtained intermediate 3 with iodine monochloride by electrophilic substitution reaction, and its structure is：
(4) carbazole and n-octane bromide are reacted in the presence of alkali, intermediate 4 is obtained, its structure is：
(5) intermediate 4 reacts at room temperature with N- bromo-succinimides, obtains intermediate 5, and its structure is：
(6) intermediate 5 and duplex pinacol boron ester be under the catalysis of catalyst, by Suzuki coupling reactions, in obtaining
Mesosome 6, its structure is：
(7) 2- bromines carbazole reacts with n-octane bromide in the presence of alkali, and intermediate 7 is obtained, and its structure is：
(8) intermediate 7, by Suzuki coupling reactions, is obtained with duplex pinacol borate under the catalysis of catalyst
Intermediate 8, its structure is：
(9) by paraiodoanisole and carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, intermediate is obtained
10, its structure is：
(10) intermediate 9 and N- bromo-succinimides are reacted, obtains intermediate 9, its structure is：
(11) by paraiodoanisole and 2- bromines carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, in being obtained
Mesosome 11, its structure is：
(12) by intermediate 10 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions,
Intermediate 12 is obtained, its structure is：
(13) by intermediate 11 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions,
Intermediate 13 is obtained, its structure is：
(14) by 4- (9H- carbazole -9- bases) phenyl boric acids and intermediate 3 under the catalysis of catalyst, it is coupled by Suzuki
Reaction, is obtained intermediate 14, and its structure is：
(15) it is anti-by Suzuki couplings respectively by intermediate 6,8,12,13 and intermediate 3 under the catalysis of catalyst
Should, intermediate 15,16,17,18 is obtained, its structure is：
(16) intermediate 14~18 is obtained target dye molecule respectively with cyanoacetic acid by Knoevenagel condensation reactions
Dye 1-5, its structure is：
Used as the preferred of above-mentioned technical proposal, in step (1)-(15), the reaction medium of the reaction is N, N- dimethyl
One or more mixing of formamide, tetrahydrofuran, dichloromethane, ethyl acetate, toluene, chloroform, ethanol.
It is described to urge in step (6), (8), (11), (12), (13), (14), (15) as the preferred of above-mentioned technical proposal
Agent is Pd (PPh3)4、Pd(dppf)Cl2, one kind in CuI.
As the preferred of above-mentioned technical proposal, the step (2), (6), (8), (9), (11), (12), (13), (14),
(15), the reaction temperature in (16) is 75-120 DEG C, and the reaction time of step (1)-(15) is 5-48h.
Compared with prior art, the invention has the advantages that：
(1) in synthetic method, the method raw material is commonly easy to get, and low production cost, reaction condition is more easy to control, and product is pure
Abbreviation list, the yield with universality, and product is greatly improved；
(2) by the spectral data analysis to dyestuff, we can see that such dyestuff has good photon capture energy
Power, has UV absorption scope wide compared to the dyestuff of document report, DSSC is applied to, with high
Photovoltage and fill factor, curve factor.
Brief description of the drawings：
Fig. 1 is the nucleus magnetic hydrogen spectrum of Dye 1.
Fig. 2 is the nuclear-magnetism carbon spectrum of Dye 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of Dye 2.
Fig. 4 is the nuclear-magnetism carbon spectrum of Dye 2.
Fig. 5 is the nucleus magnetic hydrogen spectrum of Dye 3.
Fig. 6 is the nuclear-magnetism carbon spectrum of Dye 3.
Fig. 7 is the nucleus magnetic hydrogen spectrum of Dye 4.
Fig. 8 is the nuclear-magnetism carbon spectrum of Dye 4.
Fig. 9 is the nucleus magnetic hydrogen spectrum of Dye 5.
Figure 10 is the nuclear-magnetism carbon spectrum of Dye 5.
Figure 11 is ultra-violet absorption spectrums of the Dye 1-5 in dichloromethane solution.
Figure 12 is cyclic voltammetry curves of the Dye 1-5 in dichloromethane solution.
Figure 13 is the I-V curve that Dye 1-5 prepare organic dye sensitized solar cell.
Specific embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
(1) synthesis of intermediate 1
In the there-necked flask of 250mL, 2,4- dimethyl pyrroles (3.3g, 35mmol) and new steaming dichloromethane 40mL is added,
Load onto reflux condensing tube.Vacuumize, argon gas protection.Positive caproyl chloride (2.5mL, 18mmol), mixed liquor are added dropwise over syringe
It is heated to reflux 3h.Room temperature is cooled to, n-hexane dilution is stirred overnight, removal of solvent under reduced pressure.Add new steaming toluene 80mL, stirring
Uniformly, triethylamine (15mL, 113mmol) is added, after 20min, BFEE (20mL, 163mmol) is added dropwise over, is continued
Room temperature reaction 1h, reaction mixture is through removing solvent, dichloromethane solution dilution, saturated common salt washing (3 × 50mL), nothing under reduced pressure
Water magnesium sulfate is dried.Crude on silica gel column chromatography obtains red brown solid.1H NMR(400MHz,CDCl3)δ6.05(s,1H),
2.96-2.90 (m, 1H), 2.51 (s, 3H), 2.41 (s, 3H), 1.62 (d, J=6.6Hz, 1H), 1.46 (d, J=6.8Hz,
1H), 1.42-1.35 (m, 1H), 0.93 (t, J=6.7Hz, 2H)13C NMR(101MHz,CDCl3)δ:153.70,146.74,
140.32,131.45,121.55,32.59,31.65,28.46,22.53,16.36,14.47,14.45,14.42,14.06.
(2) synthesis of intermediate 2
In the there-necked flask of 100mL, 10mL DMFs are added, vacuumized, lead to argon gas protection, will reacted
During bottle is as ice-water bath, POCl is slowly added dropwise3(6.5mL, 7.00mmol), 5min is dripped off, and reaction bulb is placed in room temperature reaction
30min.0.524g intermediates 1 are dissolved in 30mL 1,2- dichloroethanes after dripping, is warming up to 50 DEG C of reaction 2h.It is cooled to room
Temperature, reaction solution is poured slowly into unsaturated carbonate potassium solution.Dichloromethane solution is extracted, and organic phase is washed 3 times, and anhydrous magnesium sulfate is done
It is dry.Crude product obtains yellow solid through silica gel column chromatography.1H NMR(400MHz,CDCl3)δ:10.05(s,1H),6.18(s,1H),
3.03–2.93(m,2H),2.72(s,3H),2.69(s,3H),2.52(s,3H),2.43(s,3H),1.48(s,2H),1.44
(d, J=6.7Hz, 2H), 1.39-1.34 (m, 2H), 0.89 (t, J=6.9Hz, 3H)
(3) synthesis of intermediate 3
Intermediate 2 (226mg, 0.6mmol), 20mL methyl alcohol/DMF (V/V=1 are added in 50mL there-necked flasks:1).Take out true
Sky, under argon gas protection, is slowly added dropwise the methanol solution of iodine monochloride.At room temperature, continue to stir half an hour, TLC detects raw material
Total overall reaction is complete.Add 20mL water in reaction bulb, dichloromethane extracts 3 × 30mL, merges organic phase, and organic phase saturation is thio
Metabisulfite solution is washed 3 times.Organic phase anhydrous magnesium sulfate is dried, and crude on silica gel column chromatography obtains red solid, yield 65%.1H
NMR(400MHz,CDCl3)δ:10.13 (s, 1H), 3.08 (d, J=7.1Hz, 2H), 2.79 (s, 3H), 2.77 (s, 3H), 2.67
(s, 3H), 2.54 (s, 3H), 1.71-1.61 (m, 2H), 1.51 (d, J=7.6Hz, 2H), 1.41 (dd, J=14.0,7.1Hz,
2H), 0.95 (t, J=7.0Hz, 3H)13C NMR(101MHz,CDCl3)δ:186.06,159.10,156.79,149.26,
144.90,141.91,133.66,130.14,126.54,32.45,31.48,29.15,22.50,19.40,16.48,14.02,
13.18,12.88.
(4) synthesis of intermediate 4 (9- octylcarbazols)
In 250mL there-necked flasks, 5g (15.4mmol) carbazole, 100mL DMSO, 0.25g (1.1mmol) are sequentially added
TEBA and 25mL sodium hydroxide solutions (50wt%), dropwise addition (3.3g, 16.9mmol) 1- bromines are just pungent in 0.5h under magnetic agitation
Alkane, room temperature reaction 8h stops reaction, and hydrochloric acid regulation PH=7 is added in reaction solution, is extracted with ethyl acetate (3 × 50mL), merges
Organic layer and with saturated common salt water washing 3 times, anhydrous magnesium sulfate is dried overnight, distilling off solvent after filtering, residue oil
Ether is eluant, eluent column chromatography for separation, obtains pale yellowish oil liquid, yield 80%.1H NMR(400MHz,CDCl3), δ:8.15
(d, J=1.5Hz, J=8Hz, 2H), 7.50 (d, 2H), 7.45 (d, J=8Hz, 2H), 7.26 (d, 2H), 4.35 (t, J=8Hz,
2H), 1.95-1.85 (m, 2H), 1.50-1.20 (m, 10H), 0.92 (t, J=6.5Hz, 3H).
(5) synthesis of intermediate 5 (9- octyl group -3- bromines carbazole)
In 250mL single port bottles, 9- octylcarbazols 4g (24.0mmol) are sequentially added, NBS 8.5g (48.0mmol),
80mL anhydrous tetrahydro furans, under argon gas protection, after being heated to 80 DEG C of magnetic agitation reaction 24h, stop reaction, and reactant mixture is cold
But to pouring into 300mL distilled water after room temperature, it is extracted with ethyl acetate 3 times, organic layer is washed 3 times with saturated common salt again, is merged
Organic phase, anhydrous sodium sulfate drying is overnight.Remove solvent under reduced pressure, residue by silicagel column chromatography obtains pale yellowish oil
Thing, yield 70%.1H NMR(400MHz,CDCl3),δ:8.21 (s, 1H), 8.05 (d, 1H), 7.53 (d, 1H), 7.48 (d, J=
7.2Hz, 1H), 7.40 (d, 1H), 7.27 (t, J=12.0Hz, 2H), 4.26 (t, 2H), 1.84 (m, 2H), 1.25 (m, 10H),
0.85(t,3H)。
(6) synthesis of intermediate 6 (3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9- octylcarbazols)
The bromo- 9- octylcarbazols 2g (5.6mmol) of 3-, duplex pinacol boron ester 1.7g are sequentially added in 100mL there-necked flasks
(6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl2150mg (0.21mmol) and 80mL DMF, vacuumizes, argon
Under gas shielded, at 95 DEG C, magnetic agitation reacts 24h to control oil bath temperature.Stop reaction, after reactant mixture is cooled to room temperature
Pour into 200mL water, three times (50mL × 3) extracted with dichloromethane, then with saturated common salt water washing for several times, merge organic phase,
Anhydrous magnesium sulfate is dried.Remove solvent, residue petroleum ether under reduced pressure：Ethyl acetate=20:1 carries out silica gel for eluant, eluent
(200-300 mesh) column chromatography for separation, obtains yellow oily liquid, yield 70%.1H NMR(400MHz,CDCl3),δ:8.60(s,
1H), 8.13 (d, J=7.6Hz, 1H), 7.92 (d, J=8.1Hz, 1H), 7.45 (d, J=7.3Hz, 1H), 7.40 (t, J=
9.5Hz, 2H), 7.23 (d, J=7.0Hz, 1H), 4.30 (t, J=6.9Hz, 2H), 1.90-1.86 (m, 2H), 1.44 (s,
12H), 1.36-1.28 (m, 10H), 0.85 (t, J=13.6Hz, 3H).
(7) synthesis of intermediate 7 (9- octyl group -2- bromines carbazole)
In 250mL there-necked flasks, 3.8g (15.4mmol) 2- bromines carbazole, 100mL DMSO, 0.25g are sequentially added
(1.1mmol) TEBA and 25mL sodium hydroxide solutions (50wt%), is added dropwise 3.3g (16.9mmol) in 0.5h under magnetic agitation
1- bromine normal octanes, room temperature reaction 8h stops reaction, and hydrochloric acid regulation PH=7 is added in reaction solution, be extracted with ethyl acetate (3 ×
50mL), organic layer is merged and with saturated common salt water washing 3 times, anhydrous magnesium sulfate is dried overnight, distilling off solvent after filtering, surplus
Excess petroleum ether is eluant, eluent column chromatography for separation, obtains yellow oily liquid, yield 65%.1H NMR(400MHz,CDCl3,
TMS),δ:8.06 (d, J=7.2Hz, 1H), 7.94 (d, J=7.9Hz, 1H), 7.54 (s, 1H), 7.48 (t, J=6.7Hz,
1H), 7.40 (d, J=7.5Hz, 1H), 7.33 (d, J=8.0Hz, 1H), 7.28-7.20 (s, 1H), 4.24 (t, J=6.2Hz,
2H),1.97–1.77(m,2H),1.35–1.25(m,10H),1.01–0.75(t,3H).
(8) synthesis of intermediate 8 (2- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9- octylcarbazols)
The bromo- 9- octylcarbazols 2g (5.6mmol) of 2-, duplex pinacol boron ester 1.7g are sequentially added in 100mL there-necked flasks
(6.7mmol), potassium acetate 2.7g (28mmol), Pd (dppf) Cl2150mg (0.21mmol) and 80mL DMF, vacuumizes, argon
Under gas shielded, at 95 DEG C, magnetic agitation reacts 24h to control oil bath temperature.Obtain pale yellow with the method for similar synthetic intermediate 6
Color oily liquids.1H NMR(400MHz,CDCl3,TMS),δ:8.19-8.02 (m, 2H), 7.88 (s, 1H), 7.69 (d, J=
4.6Hz,1H),7.55–7.36(m,2H).,7.30–7.13(m,1H),4.47–4.24(m,2H),2.00–1.76(m,2H),
1.50–1.30(m,12H),1.30–1.14(m,10H),0.96–0.76(t,3H).
(9) synthesis of intermediate 9 (9- (4- methoxyphenyls) carbazole)
In 100mL there-necked flasks, be separately added into carbazole (1.67g, 10mmol), paraiodoanisole (2.57g, 11mmol),
Cuprous iodide (0.19g, 1mmol), potassium carbonate (2.76g, 20mmol), L-PROLINE (0.23g, 2mmol) DMSO 30mL, rise
Warm to 90 DEG C reaction 40h.Room temperature is cooled to, is diluted with water, ethyl acetate extraction.Organic layer saturated common salt is washed 3 times, anhydrous sulphur
Sour magnesium is dried, and crude product obtains white crystal, yield 68% through silica gel column chromatography.1H NMR(400MHz,CDCl3)δ:8.14
(d, J=7.6Hz, 2H), 7.45-7.37 (m, 4H), 7.33-7.24 (m, 4H), 7.10 (d, J=8.8Hz, 2H), 3.90 (s,
3H),ppm；13C NMR(100MHz,CDCl3)δ:158.83,141.35,130.28,128.55,125.81,123.08,
120.22,119.61,115.04,109.67,55.58.
(10) synthesis of intermediate 10 (9- (4- methoxyphenyls) -3- bromines carbazole)
In 100mL single port bottles, intermediate 9 (2.71g, 10mmol) is dissolved in 30mL DMFs, frozen water
Under the conditions of bath, NBS (1.96g, 11mmol) is added in batches, under argon gas protection, room temperature reaction overnight, stops reaction, and reaction is mixed
Compound is poured into 200mL distilled water, is extracted 3 times with dichloromethane, and organic layer is washed 3 times with saturated common salt again, merges organic phase,
Anhydrous sodium sulfate drying is overnight.Remove solvent under reduced pressure, residue by silicagel column chromatography is isolated with petroleum ether as eluant, eluent
White solid, yield 90%.1H NMR(400MHz,CDCl3) δ 8.22 (d, J=21.4Hz, 1H), 8.08 (d, J=6.8Hz,
1H), 7.48-7.39 (m, 4H), 7.33-7.27 (m, 2H), 7.19 (d, J=7.2Hz, 1H), 7.11 (d, J=7.0Hz, 2H),
3.92(s,3H).
(11) synthesis of intermediate 11 (9- (4- methoxyphenyls) -2- bromines carbazole)
Sequentially add 2- bromines carbazole (2.45g, 10mmol) in 100mL there-necked flasks, paraiodoanisole (2.58g,
11mmol), cuprous iodide (190mg, 1mmol), L-PROLINE (230mg, 2mmol), potassium carbonate (2.76g, 20mmol), DMSO
30mL.White crystal, yield 65% are obtained with the method for similar synthetic intermediate 9.1H NMR(400MHz,CDCl3)δ8.13(d,
J=7.1Hz, 1H), 8.01 (d, J=7.9Hz, 1H), 7.51-7.38 (m, 5H), 7.32 (d, J=7.9Hz, 2H), 7.15 (d, J
=7.1Hz, 2H), 3.95 (s, 3H)
(12) (3- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9- (4- methoxyphenyls) of intermediate 12
Carbazole) synthesis
Sequentially add intermediate 10 (0.65g, 1.85mmol) in 100mL there-necked flasks, duplex pinacol boron ester (0.80g,
2.80mmol), potassium acetate (0.73g, 7.40mmol), Pd (dppf) Cl2150mg (0.21mmol) and 20mL DMF, takes out true
Sky, under argon gas protection, at 95 DEG C, magnetic agitation reacts 24h to control oil bath temperature.Obtained with the method for similar synthetic intermediate 6
To white crystal, yield 72%.1H NMR(400MHz,CDCl3) δ 8.25 (d, J=21.4Hz, 1H), 8.18 (d, J=6.8Hz,
1H), 7.44 (dd, J=21.1,7.8Hz, 4H), 7.29 (dd, J=14.5,8.6Hz, 2H), 7.19 (d, J=7.2Hz, 1H),
(s, the 12H) of 7.11 (d, J=7.1Hz, 2H), 3.92 (s, 3H), 1.36
(13) (2- (4,4,5,5- tetramethyl -1,3,2- dioxaborolanes) -9- (4- methoxyphenyls) of intermediate 13
Carbazole) synthesis
Sequentially add intermediate 11 (0.54g, 1.54mmol) in 100mL there-necked flasks, duplex pinacol boron ester (0.57g,
2.31mmol), potassium acetate (0.59g, 6.20mmol), Pd (dppf) Cl2100mg (0.18mmol) and 20mL DMF, takes out true
Sky, under argon gas protection, at 95 DEG C, magnetic agitation reacts 24h to control oil bath temperature.Obtained with the method for similar synthetic intermediate 6
To white crystal, yield 67%.1H NMR(400MHz,CDCl3)δ8.19–8.13(m,2H),7.80–7.72(m,2H),7.46
(d, J=8.7Hz, 2H), 7.41 (d, J=7.4Hz, 1H), 7.30 (d, J=8.6Hz, 2H), 7.13 (d, J=8.6Hz, 2H),
3.94(s,3H),1.36(s,12H).
(14) synthesis of intermediate 14
4- (9H- carbazole -9- bases) phenyl boric acid (0.27g, 0.94mmol), centre are sequentially added in the there-necked flask of 100mL
Body 3 (0.43g, 0.78mmol), tetra-triphenylphosphine palladium 20mg, 20mL tetrahydrofuran/toluene (V/V=1:1), potassium carbonate
(1.38g,10mmol).Vacuumize, argon gas protection, back flow reaction 24h at 80 DEG C.Room temperature is cooled to, is diluted with water, dichloromethane
Extraction, organic phase is washed 3 times, anhydrous sodium sulfate drying.Remove solvent under reduced pressure, residue by silicagel column chromatography obtains red solid
Body, yield 72%.1H NMR(400MHz,CDCl3) δ 10.15 (s, 1H), 8.17 (d, J=7.4Hz, 2H), 7.70 (d, J=
7.2Hz, 2H), 7.52 (d, J=7.3Hz, 2H), 7.46 (d, J=6.5Hz, 4H), 7.35-7.30 (m, 2H), 3.22-3.12
(m, 2H), 2.83 (s, 3H), 2.81 (s, 3H), 2.63 (s, 3H), 2.50 (s, 3H), 1.84-1.66 (m, 2H), 1.54 (d, J=
4.6Hz, 2H), 1.47-1.40 (m, 2H), 0.96 (t, J=6.7Hz, 3H)13C NMR(101MHz,CDCl3)δ:186.34,
158.42,149.58,140.67,137.39,131.73,128.76,127.08,126.08,125.86,123.58,120.48,
120.26,119.64,116.62,109.78,109.73,32.53,31.66,28.92,22.57,15.09,14.10,14.01,
13.10,12.79.
(15) synthesis of intermediate 15
By intermediate 3 (0.24g, 0.50mmol) and intermediate 6 (0.24g, 0.60mmol) carbon in the there-necked flask of 100mL
Sour potassium (1.1g, 8.0mmol) is dissolved in the toluene of 15mL and the tetrahydrofuran of 15mL.Vacuumize, under argon gas protection, add four triphens
Base phosphine palladium.It is warming up to 80 DEG C of backflows overnight, is cooled to room temperature, rotation removes solvent.Washed several times with water, organic phase anhydrous magnesium sulfate is dried.
Crude on silica gel column chromatography obtains red brown solid, yield 70%.1H NMR(400MHz,CDCl3)δ:10.14(s,1H),8.10
(d, J=7.0Hz, 1H), 7.91 (s, 1H), 7.57-7.43 (m, 3H), 7.28 (d, J=18.7Hz, 2H), 4.33 (d, J=
6.0Hz, 2H), 3.21-3.07 (m, 2H), 2.80 (d, J=10.0Hz, 6H), 2.56 (s, 3H), 2.43 (s, 3H), 1.91 (d, J
=6.4Hz, 2H), 1.77-1.68 (m, 2H), 1.53 (d, J=3.9Hz, 2H), 1.45-1.35 (m, 6H), 1.26 (s, 6H),
0.94 (t, J=6.0Hz, 3H), 0.87 (s, 3H)13C NMR(101MHz,CDCl3)δ:186.30,160.12,155.21,
148.52,140.80,139.91,127.61,126.12,123.06,122.65,122.48,121.97,120.42,119.14,
108.97,108.84,61.91,32.50,31.83,31.61,29.41,29.22,29.06,28.82,27.37,22.65,
22.55,15.08,14.12,14.07,12.97.
(16) synthesis of intermediate 16
By intermediate 3 (0.32g, 0.70mmol) and intermediate 8 (0.33g, 0.80mmol) carbon in the there-necked flask of 100mL
Sour potassium (1.1g, 8.0mmol) is dissolved in the toluene of 20mL and the tetrahydrofuran of 20mL.Vacuumize, under argon gas protection, add four triphens
Base phosphine palladium.It is warming up to 80 DEG C of backflows overnight, is cooled to room temperature, rotation removes solvent.Washed several times with water, organic phase anhydrous magnesium sulfate is dried.
Crude on silica gel column chromatography obtains red brown solid, yield 70%.1H NMR(400MHz,CDCl3)δ:10.15(s,1H),
8.19-8.08 (m, 2H), 7.46 (dd, J=21.6,7.5Hz, 2H), 7.26 (s, 2H), 7.04 (d, J=7.6Hz, 1H), 4.31
(d, J=12.9Hz, 2H), 3.14 (s, 2H), 2.80 (d, J=9.9Hz, 6H), 2.57 (s, 3H), 2.44 (s, 3H), 1.87 (d,
J=6.6Hz, 2H), 1.78-1.63 (m, 2H), 1.52 (d, J=7.1Hz, 2H), 1.43-1.22 (m, 12H), 0.95 (t, J=
7.0Hz, 3H), 0.84 (d, J=6.6Hz, 3H)13C NMR(101MHz,CDCl3)13C NMR(101MHz,CDCl3)δ:
186.23,150.53,148.91,140.90,140.55,129.80,126.07,122.53,120.92,120.48,119.18,
110.29,108.86,32.50,31.77,31.61,29.43,29.20,29.12,28.85,27.50,22.62,22.54,
15.01,14.05,13.01,12.65.
(17) synthesis of intermediate 17
By intermediate 3 (0.35g, 0.50mmol) and intermediate 12 (0.24g, 0.60mmol) in the there-necked flask of 100mL
Potassium carbonate (1.1g, 8.0mmol) is dissolved in the toluene of 15mL and the tetrahydrofuran of 15mL.Vacuumize, under argon gas protection, add four or three
Phenylphosphine palladium.It is warming up to 80 DEG C of backflows overnight, is cooled to room temperature, rotation removes solvent.Washed several times with water, organic phase anhydrous magnesium sulfate is done
It is dry.Crude on silica gel column chromatography obtains red brown solid, yield 70%.1H NMR(400MHz,CDCl3)δ10.14(s,1H),
8.14 (d, J=7.6Hz, 1H), 7.96 (s, 1H), 7.49 (d, J=8.6Hz, 2H), 7.45-7.34 (m, 3H), 7.30 (t, J=
7.3Hz, 1H), 7.21 (d, J=8.3Hz, 1H), 7.14 (d, J=8.5Hz, 2H), 3.94 (s, 3H), 3.24-3.07 (m, 2H),
2.81(s,3H),2.79(s,3H),2.57(s,3H),2.44(s,3H),1.80–1.67(m,2H),1.55–1.49(m,2H),
1.45-1.40 (m, 2H), 0.95 (t, J=7.1Hz, 3H)13C NMR(101MHz,DMSO)δ:186.29,159.08,
148.64,141.78,140.87,130.02,128.55,127.90,126.39,125.85,123.70,123.40,122.77,
121.89,120.34,120.07,115.21,110.01,77.39,77.07,76.75,55.67,32.51,31.63,28.84,
22.56,15.07,14.07,13.00,12.61.
(18) synthesis of intermediate 18
By intermediate 3 (0.15g, 0.50mmol) and intermediate 13 (0.24g, 0.60mmol) in the there-necked flask of 100mL
Potassium carbonate (1.1g, 8.0mmol) is dissolved in the toluene of 15mL and the tetrahydrofuran of 15mL.Vacuumize, under argon gas protection, add four or three
Phenylphosphine palladium.It is warming up to 80 DEG C of backflows overnight, is cooled to room temperature, rotation removes solvent.Washed several times with water, organic phase anhydrous magnesium sulfate is done
It is dry.Crude on silica gel column chromatography obtains red brown solid, yield 70%.1H NMR(400MHz,CDCl3)δ:10.13(s,1H),
8.20 (d, J=7.9Hz, 2H), 7.45 (dd, J=12.6,8.3Hz, 3H), 7.38-7.28 (m, 2H), 7.15-7.08 (m,
4H), 3.91 (s, 3H), 3.11 (d, J=5.6Hz, 2H), 2.80 (s, 3H), 2.77 (s, 3H), 2.52 (s, 3H), 2.39 (s,
3H), 1.77-1.61 (m, 2H), 1.53-1.48 (m, 2H), 1.40 (dd, J=14.3,7.1Hz, 2H), 0.93 (t, J=
7.1Hz,3H).13C NMR(101MHz,DMSO)δ:186.26,159.06,155.48,148.87,141.86,141.48,
130.15,129.97,128.50,126.33,122.76,121.83,120.39,120.08,115.26,111.21,109.90,
77.39,77.07,76.76,55.64,32.49,31.56,28.81,22.53,15.00,14.06,13.00,12.65.
Embodiment 1
(1) synthesis of Dye 1：
To sequentially added in the there-necked flask of 100mL intermediate 14 (180mg, 0.3mmol), cyanoacetic acid (50mg,
0.6mmol), acetonitrile (20mL), chloroform (20mL) and piperidines (0.2mL), under argon gas protection, 80 DEG C of backflow 24h.It is cooled to room
Temperature, reaction solution is poured into 50mL dichloromethane and diluted, and washes 3 times (3 × 50mL), and the anhydrous MgSO4 of organic phase is dried.Rotary evaporation
Remove solvent, crude on silica gel column chromatography (dichloromethane：Methyl alcohol=10:1) 156mg dark red solid powder, yield, are obtained
80%.1H NMR(400MHz,CDCl3) δ 10.15 (s, 1H), 8.17 (d, J=7.4Hz, 2H), 7.70 (d, J=7.2Hz, 2H),
7.51 (s, 2H), 7.46 (d, J=6.5Hz, 4H), 7.32 (s, 2H), 3.17 (t, 2H), 2.83 (s, 3H), 2.81 (s, 3H),
2.63 (s, 3H), 2.50 (s, 3H), 1.74 (s, 2H), 1.54 (d, J=4.6Hz, 2H), 1.43 (d, J=6.5Hz, 2H), 0.96
(t,3H).13C NMR(101MHz,CDCl3)δ:186.34,158.42,149.58,140.67,137.39,131.73,
128.76,127.08,126.08,125.86,123.58,120.48,120.26,119.64,116.62,109.78,109.73,
32.53,31.66,28.92,22.57,15.09,14.10,14.01,13.10,12.79.MALDI-TOF-MS,m/z:calcd
for C39H35BF2N4O2[M]+:654.300,found:654.318.
Embodiment 2
(2) synthesis of Dye 2：
150mg aubergine solid powders, yield 78% are obtained with the method similar to synthetic dyestuffs 1.1H NMR
(600MHz,DMSO)δ:8.21 (d, J=7.7Hz, 2H), 8.12 (s, 1H), 7.67-7.69 (d, J=7.7Hz, 2H), 7.62
(d, J=7.7Hz, 2H), 7.47 (d, J=9.8Hz, 2H), 7.36 (d, J=7.2Hz, 2H), 7.19-7.24 (t, J=7.3Hz,
2H),3.12(s,2H),2.47(s,3H),2.46(s,3H),2.43(s,3H),2.41(s,3H),1.79(m,2H),1.65(m,
2H), 1.49 (m, 2H), 0.90 (t, J=7.0Hz, 3H)13C NMR(151MHz,DMSO)δ:174.83,172.89,140.75,
140.49,137.63,133.49,132.47,131.41,131.32,130.12,126.81,126.68,126.48,123.29,
123.07,120.93,120.32,110.29,110.23,32.94,31.75,29.49,22.56,15.43,14.49,14.42,
13.64,13.22.MALDI-TOF-MS,m/z:calcd for C42H49BF2N4O2[M]+:690.400,found:690.251.
Embodiment 3
The synthesis of Dye 3
145mg aubergine solid powders, yield 75% are obtained with the method similar to synthetic dyestuffs 1.1H NMR
(600MHz,DMSO)δ:8.20 (d, J=6.5Hz, 1H), 8.17 (d, J=6.8Hz, 1H), 7.91 (s, 1H), 7.60-7.55
(m, 2H), 7.46 (t, J=7.3Hz, 1H), 7.21 (t, J=7.1Hz, 1H), 7.09 (d, J=6.7Hz, 1H), 4.41 (s,
2H),3.09(s,2H),2.48(s,6H),2.41(s,6H),1.76(s,2H),1.65(s,2H),1.48(s,2H),1.37(d,
J=6.6Hz, 2H), 1.23-1.13 (m, 10H), 0.90 (t, J=6.8Hz, 3H), 0.78 (t, J=6.6Hz, 3H)13C NMR
(151MHz,DMSO)δ:155.41,151.10,148.38,140.81,140.66,139.06,137.58,135.96,
132.25,131.06,130.20,126.32,126.03,122.34,121.75,121.27,120.83,120.72,119.31,
111.52,109.77,51.60,32.81,32.35,31.57,29.26,29.23,29.11,29.08,27.05,22.50,
22.29,15.40,14.77,14.35,14.32,13.92,13.13.MALDI-TOF-MS,m/z:calcd for
C42H49BF2N4O2[M]+:690.400,found:690.612.
Embodiment 4
The synthesis of Dye 4
160mg red solid powder, yield 82% are obtained with the method similar to synthetic dyestuffs 1.1H NMR(600MHz,
DMSO)δ:8.30 (s, 1H), 8.24 (s, 1H), 7.79 (s, 1H), 7.59 (d, J=8.7Hz, 2H), 7.46 (t, J=7.7Hz,
1H), 7.38 (t, J=6.5Hz, 2H), 7.31 (dd, J=13.0,7.9Hz, 2H), 7.25 (d, J=8.8Hz, 2H), 3.90 (s,
3H), 3.21-3.09 (m, 1H), 2.47 (s, 3H), 2.46 (s, 3H), 2.44 (s, 3H), 2.43 (s, 3H), 1.69 (dd, J=
15.7,7.8Hz, 2H), 1.55-1.49 (m, 2H), 1.40 (dd, J=14.7,7.3Hz, 2H), 0.92 (t, J=7.3Hz, 3H)
.13C NMR(151MHz,DMSO)δ:166.51,162.78,159.11,155.30,148.24,141.46,140.37,
138.98,137.39,132.10,130.16,129.70,128.78,126.94,126.30,124.39,123.24,122.87,
120.41,119.93,119.53,115.83,112.56,110.11,110.03,109.82,109.31,55.97,33.00,
32.37,31.56,22.33,15.38,14.82,14.43,14.39,13.19.MALDI-TOF-MS,m/z:calcd for
C41H39BF2N4O3[M]+:684.300,found:684.700.
Embodiment 5
The synthesis of Dye 5：
148mg red brown solid powder, yield 78% are obtained with the method similar to synthetic dyestuffs 1.1H NMR
(600MHz,DMSO)δ:8.35 (d, J=7.9Hz, 1H), 8.30 (d, J=7.6Hz, 1H), 7.78 (s, 1H), 7.57 (d, J=
8.8Hz, 2H), 7.46 (t, J=7.9Hz, 1H), 7.32 (dd, J=16.0,7.9Hz, 2H), 7.22 (d, J=8.7Hz, 3H),
7.15 (s, 1H), 3.87 (s, 3H), 3.11 (t, J=10.4Hz, 1H), 2.44 (s, 3H), 2.41 (s, 6H), 2.38 (s, 3H),
1.69-1.61 (m, 2H), 1.49-1.45 (m, 2H), 1.38 (dd, J=13.7,6.4Hz, 2H), 0.90 (t, J=7.3Hz,
3H).13C NMR(151MHz,DMSO)δ:162.63,160.84,159.03,156.18,151.35,148.58,141.52,
141.13,137.77,135.55,130.84,129.97,129.60,128.68,126.90,122.73,122.53,122.30,
121.12,120.50,115.87,111.45,110.10,55.92,32.34,31.41,29.50,22.28,15.46,14.77,
14.37,14.26,13.89.MALDI-TOF-MS,m/z:calcd for C41H39BF2N4O3[M]+:684.300,found:
684.699.
Ultra-violet absorption spectrums and electrochemistry of the target dyestuff Dye 1~5 in dichloromethane solution in above-described embodiment
The related data of matter is shown in Table 1, and the photoelectric properties parameter of target dyestuff Dye 1~5 is shown in Table 2 in embodiment.
The optical physics and electrochemical data of the Dye 1~5 of table 1
[a]In CHCl3 solutions.
[b]Absorption maximum on TiO2was obtained through measuring the dyes
adsorbed on 3μm TiO2 nanoparticle films in a CHCl3 solution.
[c]EOX was measured in CH2Cl2 and calibrated with ferrocene as an
external reference.
[d]E0,0was estimated from the absorption thresholds from absorption
spectra of dyes adsorbed on the TiO2 film.
[e]Computed from the formula E* ox=EOX-E0,0.
It can be seen that the maximal ultraviolet absorption peak of five kinds of dyestuffs is both present in 530nm or so from table 1, compared to BODIPY
Mother nucleus structure (498nm) occurs in that obvious Red Shift Phenomena, and effective conjugate length of this explanation molecule increases, the electricity of intramolecular
Son migration enhancing.When dye molecule absorption is in TiO2On film, there is faint basket and moves in maximal ultraviolet absorption peak, and this illustrates dye
Material molecule is in nanocrystalline TiO2There is deprotonation effect and H- aggregations in surface.The suction of Dye 4 and Dye 5 as seen from Figure 11
Receive spectrum it is wider, absorption intensity is bigger, this illustrate N- phenyl substitution carbazole be connected with BODIPY parent nucleus generate it is stronger
Conjugation, effective conjugate length of molecule increases, the electron transfer enhancing of intramolecular, the electron donation enhancing of D structures.With
Upper result shows that such BODIPY dye molecule has good photon capture ability, possesses and musts as dye sensitizing agent
The spectral conditions for needing.5 kinds of ground state oxidizing potential (E of dyestuff can also be found out from table 1oxVs.NHE I) is compared3-/I-Electricity to
Oxidation/reduction current potential (0.42V vs.NHE) is corrected, that is, the oxidation state dye molecule for losing electronics can effectively by I-Reduction；Dye
Expect that energy level (- 0.5V vs.NHE) of the excitation state reduction potential of molecule than the conduction band of titanium dioxide is more negative, can just make excitation state
Electronics be efficiently injected into the conduction band of semiconductor, so electronic circulation based on dye cell is fully utilized, thus
These BODIPY dyestuffs can be as the sensitizer of titanium dioxide electrodes.
The photoelectric properties parameter of the Dye 1~5 of table 2
Five kinds of dye molecules are in AM1.5 (100mWcm-2) simulated solar irradiation under, based on Dye 1-5 sensitization solar energy
Current-voltage (J-V) curve of battery is as shown in figure 13, corresponding short circuit current (Jsc), open-circuit voltage (Voc), fill factor, curve factor
Etc. (FF) battery parameter is listed in table 2.The J of the solar cell device of the sensitizations of Dye 4scIt is 5.40mAcm-2, Voc is 600mV,
FF values are 0.70.So that the battery parameter of Dye 4 is probably 3- of carbazole ring the reason for higher being connected with BODIPY units, give
Electronic center is more beneficial for photoelectronic intramolecular migration closer to receptor unit；Secondly because N- methoxyphenyls take
The carbazole electron donation in generation is stronger, thus Dye 4 has photoelectric current higher and photovoltage value.
The present invention illustrates detailed synthetic method by above-described embodiment, but the invention is not limited in the above method, i.e.,
Do not mean that the present invention has to rely on above-mentioned reaction condition and could implement.Person of ordinary skill in the field is it will be clearly understood that right
Any improvement of the invention, the change of equivalence replacement and reaction actual conditions to reaction dissolvent catalyst of the present invention etc., fall
Within the scope of protection scope of the present invention and disclosure.
Claims (5)
1. one kind 2,6- organic dye sensitized dose of the BODIPY class of substitution, it is characterised in that the chemical constitution with formula I：
In formula I, D is donor monomer, is the one kind in following construction unit：
Wherein, R1It is H or alkyl or alkoxy, n is 5；
A is receptor unit, is the one kind in following construction unit：
2. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 1, its spy
Levy and be, comprise the following steps：
(1) be there is into condensation reaction in 2,4- dimethyl pyrroles and acyl chlorides, then complex reaction is carried out with BFEE, in being obtained
Mesosome 1, its structure is：
(2) intermediate 1 obtains intermediate 2 by dimension David Smail formylation reaction, and its structure is：
(3) intermediate 2 is obtained intermediate 3 with iodine monochloride by electrophilic substitution reaction, and its structure is：
(4) carbazole and n-octane bromide are reacted in the presence of alkali, intermediate 4 is obtained, its structure is：
(5) intermediate 4 reacts at room temperature with N- bromo-succinimides, obtains intermediate 5, and its structure is：
(6) intermediate 5, by Suzuki coupling reactions, obtains intermediate with duplex pinacol boron ester under the catalysis of catalyst
6, its structure is：
(7) 2- bromines carbazole reacts with n-octane bromide in the presence of alkali, and intermediate 7 is obtained, and its structure is：
(8) intermediate 7, by Suzuki coupling reactions, obtains centre with duplex pinacol borate under the catalysis of catalyst
Body 8, its structure is：
(9) by paraiodoanisole and carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, intermediate 9 is obtained, its knot
Structure is：
(10) intermediate 9 and N- bromo-succinimides are reacted, obtains intermediate 10, its structure is：
(11) by paraiodoanisole and 2- bromines carbazole under the catalysis of catalyst, by Liv Ullmann condensation reaction, intermediate is obtained
11, its structure is：
(12) by intermediate 10 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions, it is obtained
Intermediate 12, its structure is：
(13) by intermediate 11 and duplex pinacol borate under the catalysis of catalyst, by Suzuki coupling reactions, it is obtained
Intermediate 13, its structure is：
(14) by 4- (9H- carbazole -9- bases) phenyl boric acids and intermediate 3 under the catalysis of catalyst, by Suzuki coupling reactions,
Intermediate 14 is obtained, its structure is：
(15) respectively by intermediate 6,8,12,13 and intermediate 3 under the catalysis of catalyst, by Suzuki coupling reactions, system
Intermediate 15,16,17,18 is obtained, its structure is：
(16) intermediate 14~18 is obtained target dye molecule Dye1- respectively with cyanoacetic acid by Knoevenagel condensation reactions
5, its structure is：
Wherein, n is 5.
3. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy
Levy and be, in step (1)-(15), the reaction medium of the reaction is DMF, tetrahydrofuran, dichloromethane,
One or more mixing of ethyl acetate, toluene, chloroform, ethanol.
4. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy
Levy and be, in step (6), (8), (11), (12), (13), (14), (15), the catalyst is Pd (PPh3)4、Pd(dppf)
Cl2, one kind in CuI.
5. 2,6- preparation method of organic dye sensitized dose of the BODIPY classes for replacing of one kind as claimed in claim 2, its spy
Levy and be, the reaction temperature in the step (2), (6), (8), (9), (11), (12), (13), (14), (15), (16) is 75-
120 DEG C, the reaction time of step (1)-(15) is 5-48h.
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