CN102532121B - Rhodanine derivative and application thereof - Google Patents

Rhodanine derivative and application thereof Download PDF

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CN102532121B
CN102532121B CN201210003358.0A CN201210003358A CN102532121B CN 102532121 B CN102532121 B CN 102532121B CN 201210003358 A CN201210003358 A CN 201210003358A CN 102532121 B CN102532121 B CN 102532121B
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compound
formula
rhodanine
group
taken
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CN102532121A (en
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花建丽
毛江毅
郭福领
贺楠楠
武文俊
应伟江
田禾
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East China University of Science and Technology
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a rhodanine derivative and an application thereof. In the rhodanine derivative, a group containing a multi-ring aromatic ring group or/and a multi-ring heteroaromatic ring group is taken as an electron donor, and 2-(1',1'-dicyan)rhodanine is taken as an electron acceptor; or a group containing a multi-ring aromatic ring group or/and a multi-ring heteroaromatic ring group is taken as an electron donor, 2-(1',1'-dicyan)rhodanine is taken as an electron acceptor, and a conjugated heteroaromatic ring group is taken as a bridging group. The obtained rhodanine derivatives have unique photoelectric chemical performance, and can be taken as photosensitizers of dye-sensitized solar cells.

Description

Rhodanine derivates and uses thereof
Technical field
The present invention relates to a kind of Rhodanine derivates and uses thereof, specifically, relate to a kind of based on propane dinitrile Rhodanine derivates and uses thereof.
Background technology
Be accompanied by the develop rapidly of mankind's industrial civilization and market economy, the mineral Nonrenewable resources such as coal, oil and natural gas are day by day exhausted, and the energy dilemma and the environmental pollution that cause have thus become globalization problem urgently to be resolved hurrily.Therefore people are in the urgent need to finding other new alternative energy.Dye sensitization solar battery (B.O ' Regan, M. nature, 1991,353,737-740), because it has with low cost and makes the potential practical values of advantage such as simple.
Dye sensitization solar battery (Dye-sensitized Solar Cells, DSSCs) is conventionally by the oxide semiconductor film (TiO of nanoporous 2), dye sensitizing agent, redox electrolytes matter (I -/ I 3-) and to compositions such as electrodes (Pt), to the transmission of the receptivity of sunlight and electronics, be wherein the core of whole DSSCs system.The best light-sensitive coloring agent of photoelectric transformation efficiency is bipyridyl ruthenium complex compound (approximately 12%) up to now, but because ruthenium is expensive as rare metal, and the preparation process of dye sensitizing agent is more complicated.Therefore, find important content low-cost, that base metal class organic photovoltaic cell sensitized material that be easy to preparation and have an applications well performance becomes current research.
Summary of the invention
The present inventor finds: take containing many cyclophanes cyclic group or/and the group of many cyclophanes heterocyclic radical (as (but being not limited to): the carbazyl of the phenothiazinyl that the triphenylamine base that triphenylamine base, alkyl or alkoxyl group replace, phenothiazinyl, alkyl replace, carbazyl, replacement, fluorenyl or replace fluorenyl etc.) be electron donor(ED), with 2-(1 ', 1 '-dicyano) rhodanine as electron acceptor(EA); Or take containing many cyclophanes cyclic group or/and the group of many cyclophanes heterocyclic radical is electron donor(ED), with 2-(1 ', 1 '-dicyano) rhodanine is as electron acceptor(EA), take conjugation aromatic heterocyclic as bridge chain base, the Rhodanine derivates obtaining, they all have unique photoelectrochemical behaviour, and can effectively be adsorbed on the titanium dioxide (TiO of nanoporous 2) on film, obtain higher photoelectric transformation efficiency.
In addition, the Rhodanine derivates that provides of invention is easy to preparation and synthetic cost well below bipyridyl ruthenium complex compound, can effectively reduce dye sensitization solar battery cost.
Rhodanine derivates of the present invention, its structure is suc as formula shown in I:
In formula I, A is for containing a plurality of aromatic ring yls or a plurality of replacement aromatic ring yl, or/and the group of one or more aromatic heterocyclics of one or more aromatic heterocyclic or replacement; L is one or more conjugation aromatic heterocyclic of divalence; M is 0 or 1.
The present invention also discloses a kind of purposes of compound shown in formula I, and it can be used as the application of the photosensitizers of dye sensitization solar battery.
Accompanying drawing explanation
Fig. 1 is the prepared Compound I-1～I-4 of embodiment 1～5 and the ultraviolet-ray visible absorbing spectrogram of comparison CA-1 in methylene dichloride,
Wherein, what X-coordinate represented is wavelength (unit is nanometer), and what ordinate zou represented is molar extinction coefficient (unit is for rising every mole every centimetre).
Fig. 2 is Compound I-1～I-4 and the ultraviolet-ray visible absorbing spectrogram of comparison CA-1 on titanium dioxide film,
Wherein, what X-coordinate represented is wavelength (unit is nanometer), and what ordinate zou represented is molar extinction coefficient (unit is for rising every mole every centimetre).
Fig. 3 be take the I-V curve of the solar cell that Compound I-1～I-4 and comparison CA-1 be photosensitizer,
Wherein, what X-coordinate represented is voltage (unit is volt), and what ordinate zou represented is current density (unit is every square centimeter of milliampere).
Embodiment
In preferred technical scheme of the present invention, A is C 1～C 20the triphenyl amido that the alkyl of straight or branched or alkoxyl group replace, or C 1～C 20the phenothiazinyl that the alkyl of straight or branched or alkoxyl group replace;
In a preferred technical scheme, A is C 8～C 20the triphenyl amido that the alkyl of straight or branched or alkoxyl group replace, or C 8～C 20the phenothiazinyl that the alkyl of straight or branched or alkoxyl group replace;
In a further preferred technical scheme, A is group shown in formula II or formula III:
Wherein, R 1, R 2and R 3independently be selected from respectively: C 8～C 20a kind of in the alkyl of straight or branched or alkoxyl group, curve representation replaces position;
Preferred R 1and R 2independently be selected from respectively: C 8～C 20a kind of in the alkoxyl group of straight or branched, preferred R 3for C 8～C 20the alkyl of straight or branched;
Best R 1and R 2be CH 3(CH 2) 7o-, best R 3for n-octyl.
In another optimal technical scheme of the present invention, L is group shown in formula IV:
In formula IV, X is S or O, and n is 0 or 1, and curve representation replaces position.
By following method, or/and can making, strategy invents described Rhodanine derivates (compound shown in formula I):
(1) in preparation formula I, m is the method for 0 affiliated compound, and it comprises the steps:
(A) under the condition existing at rare gas element, rhodanine and propane dinitrile are placed in to dehydrated alcohol, and keep at least 12 hours under reflux state, stopped reaction, is cooled to room temperature, revolves to steam to remove etoh solvent, dichloromethane extraction three times, merge organic phase and be spin-dried for, then with dehydrated alcohol, carrying out recrystallization, obtaining intermediate A (compound shown in formula V);
(B) under the condition of 5% aqueous sodium hydroxide solution and rare gas element existence, compound shown in aromatic aldehyde compounds (A-CHO, the definition of A as mentioned before) and formula V is placed in to ethanol, and keeps at least 6 hours under reflux state, stopped reaction, be cooled to room temperature, revolve to steam and remove etoh solvent, dichloromethane extraction three times, merge organic phase, revolve and steam except desolventizing, then carry out column chromatography, obtain target compound (in formula I, m is 0 affiliated compound).
(2) in synthesis type I, m is that the strategy of compound is under 1, first by compd A-Br (definition of A as mentioned before) or A '-Br (its structure is suc as formula shown in VI), reacted with compound shown in formula VII, obtain intermediate B (its structure is suc as formula shown in VIII); Then by compound shown in formula VIII, reacted with compound shown in formula V, obtain target compound (in I, m is compound under 1), the concrete steps listed embodiment that vide infra.
Wherein, the implication of X, n and A is with described identical above.
The dye sensitization solar battery that the Rhodanine derivates of the present invention (compound shown in formula I) of take is photosensitizers is mainly by light anode, photocathode and their substrate and electrolyte ingredient; The material of light anode and photocathode substrate is conductive glass, is covered with the transparent plastics of conducting film above; Photo-anode substrate work area one example is provided with nanoporous TiO 2film, and be impregnated with I-1～I-4 and comparison CA-1; Photocathode substrate work area one side is provided with catalyst layer; Light anode and photocathode relative spacing arrange, and periphery forms airtight cavity with sealing material sealing, is filled with ionogen in cavity.
A method of preparing above-mentioned dye sensitization solar battery, comprises the steps:
A. clean conductive glass: FTO conductive glass is slit into 1.2 * 1.8cm, uses successively glass cleaner, clear water, acetone, intermediate water, washing with alcohol, dry up, stand-by.
B. platinized electrode: conductive glass surrounding is clung with adhesive plaster, conducting surface upward, the aqueous isopropanol (2 * 10 of spin coating Platinic chloride on conductive glass -4m), after infrared lamp is dried, 400 ℃ are dried 15min, after cooling, make a call in position a hole, standby.
C. the preparation of dyestuff (compound shown in formula I) solution: with methylene dichloride preparation 3 * 10 -4the dye solution of M.
D. the preparation of light anode: brush one deck TiO by silk screen printing (0.5 * 0.5cm) on FTO conductive glass 2slurry, 125 ℃ are dried 6 minutes, cooling after, then be coated with one deck, 125 ℃ are dried 6min, are coated with altogether two-layerly, are then slowly warming up to 450 ℃ and dry 15min, then be warming up to 500 ℃ and dry 15min, are cooled to after room temperature, with the TiCl of 20mM 4aqueous solution room temperature treatment 12h, respectively by secondary washing, washing with alcohol, 450 ℃ are dried 30min, are steeped in dye solution (being prepared by step c) after cooling.After 12h, take out, with soaking the washing of dyestuff solvent for use, dry up.
E. electrolytical preparation: the acetonitrile of crossing with Non-aqueous processing and 2-methyl propionitrile are that the preparation of 9/1 mixed solvent contains 0.05M I by volume 2, 0.15M LiI, 0.1M DMPII and 0.5M TBP solution 10mL.
F. the encapsulation of battery: at the TiO that has adsorbed dyestuff 2heat curing-type rubber belt sealing circle sticks in the surrounding of film, to the conducting surface of electrode towards inner cap at TiO 2on film, aperture is in TiO 2the gap location of film and heat curing-type rubber belt sealing circle, with the encapsulation of battery packaging machine heating and pressurizing; In aperture, inject ionogen, vacuum is extracted the bubble of cell active area out, and ionogen is fully filled in the cavity of two electrodes, and finally sealed, makes dye sensitization solar battery.
The test of above-mentioned dye sensitization solar battery:
From light anode and the photocathode of tested battery, draw respectively wire, receive on battery performance test device, the working area of battery is determined by the square hole splicing tape of a 0.5 * 0.5cm, by solar simulator (91160 types, Newport, USA) simulated solar irradiation, by light intensity regulating to 100mW/cm 2, the photoelectric transformation efficiency recording is 3.46～7.04%, short-circuit current is 8.63～13.64mA cm -2, open circuit voltage is 0.634～0.804V, packing factor is 0.63～0.72 (referring to embodiment 8).
Propane dinitrile Rhodanine derivates provided by the invention, it not only has good solubility, and can also effectively prevent the generation of dark current.With respect to existing noble metal complexes photosensitizers, the invention provides propane dinitrile Rhodanine derivates and there is synthetic simple, low cost and other advantages.
The present invention simultaneously applies very general cyanoacetic acid first as electron acceptor(EA) in propane dinitrile rhodanine group replaces organic dye sensitized dose, and itself and the compound that contains cyanoacetic acid are contrasted, experiment finds that the organic dye based on propane dinitrile rhodanine has higher photoelectric transformation efficiency.This provides new direction for the research work of organic dye sensitized dose from now on.
Below by embodiment, the present invention is further elaborated, and its object is only better to understand content of the present invention.Therefore, for example do not limit the scope of the invention:
In the following example, said room temperature refers to 20 ℃～25 ℃, and raw material and reagent used are commercially available product.
Embodiment 1
In 100ml there-necked flask, add rhodanine (2.66g, 20mmol), propane dinitrile (1.32g, 20mmol), sodium-acetate (1.64g, 20mmol) and dehydrated alcohol (60ml), reflux 12h under Ar protection.After reaction finishes, revolve to steam and remove etoh solvent, remaining solid dichloromethane extraction 3 times, merge organic phase and also with revolving after anhydrous magnesium sulfate drying to steam, remove methylene dichloride, then with dehydrated alcohol, carry out recrystallization, obtain product 1.98g, productive rate 60%.
1H?NMR(400MHz，DMSO)δ：3.78(s，2H).HR-MS(EI)calculated?for?C 6H 3N 3OS：163.9919，found：163.9918.
In 250ml there-necked flask, add thiodiphenylamine (10g, 50mmol), 5g sodium hydroxide (5g, 0.1mol) and DMSO (100ml), then add 1.6g tetra-n-butyl ammonium bromide (1.6g, 5mmol), and 30min is at room temperature stirred in reaction.Then slowly drip (at least 20min) 1-bromooctane (16.62g, 55mmol), at room temperature stirring reaction 24h.After reaction finishes, reaction solution is poured into water, limit bevelling stirs, dichloromethane extraction 3 times, the anhydrous MgSO of extraction liquid 4dry, be spin-dried for, then carry out column chromatography (PE).Obtain colourless liquid 12.6g, productive rate 81%.
1H?NMR(400MHz，CDCl 3)δ：7.11-7.09(m，4H)，6.89-6.80(dd，4H)，3.80-3.77(t，2H)，1.77(d，2H)，1.37-1.24(m，10H)，0.87(t，3H).
In 100ml there-necked flask, add compound 1 (3.11g, 10mmol) and DMF (3.65g, 0.05mol), under condition of ice bath, in flask, slowly drip (at least 30min) POCl 3(7.68g, 0.05mol), after dropwising, under Ar protection, is warming up to rapidly 90 ℃ of stirring reaction 6h.After reaction finishes, reaction solution is slowly poured in frozen water, solution is neutralized to PH >=10 with sodium hydroxide, has immediately a large amount of dark red solid to separate out, and filters.Solid is dissolved in appropriate DCM, extracts 3 times.Organic layer is spin-dried for, and then puts into vacuum drying oven and is dried, and finally carries out column chromatography (PE: DCM=3: 1) obtain sticky shape yellow liquid 1.46g, productive rate 43%.
1H?NMR(400MHz，CDCl 3)δ：9.79(s，1H)，7.64(dd，J＝8.4，1.9Hz，1H)，7.58(d，J＝1.9Hz，1H)，7.19-7.07(m，2H)，7.00-6.83(m，3H)，3.96-3.74(m，2H)，1.89-1.73(m，2H)，1.49-1.37(m，2H)，1.28(dd，J＝14.4，7.9Hz，9H)，0.87(t，3H).
In 100ml there-necked flask, add compound 2 (339mg, 1mmol), compd A (165mg, 1mmol), 5% aqueous sodium hydroxide solution (0.3mI).Under Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, then use dichloromethane extraction 3 times, merge organic phase and with anhydrous magnesium sulfate drying, revolve to steam and obtain crude product except desolventizing, finally carry out column chromatography (EtOH/DCM=10: 1), obtain red solid 370mg, productive rate 76%.
1H?NMR(400MHz，CDCl 3)δ：7.40(s，1H)，7.36(s，1H)，7.30(s，1H)，7.20-7.06(m，3H)，7.01(s，1H)，6.92(s，1H)，3.90(s，2H)，1.47(s，2H)，1.26(t，J＝7.4Hz，10H)，0.88(t，3H).
Embodiment 2
In 250ml there-necked flask, add to iodophenol (8.8g, 40mmol) 1-bromooctane (8ml, 44mmol), salt of wormwood (10.04g, 80mmol) and potassiumiodide (6g, 40mmol).Under Ar protection, add 80ml DMF, be warming up to 90 ℃ of stirring reaction 24h.After reaction finishes, reaction solution is poured into and in frozen water, is stirred to ice and melts completely, CH 2cl 2extraction, washing, organic phase has anhydrous sodium sulfate drying, is spin-dried for solvent, then carries out column chromatography (PE).Obtain colourless liquid 9.6g, productive rate 72.3%.
1H?NMR(400MHz，CDCl 3)δ：7.94(s，2H)，6.68(s，2H)，4.10(s，2H)，1.73(s，2H)，1.43(s，2H)，1.28(d，J＝19.9Hz，8H)，0.89(s，3H).
In 250ml there-necked flask, add pentanoic (1.4g, 15mmol), 3 (25.2g, 76mmol), phenanthroline (2.97g, 15mmol), cuprous chloride (2.87g, 15mmol), potassium hydroxide (3.36g, 60mmol), toluene (80ml).Back flow reaction 48h under Ar protection.After reaction finishes, be spin-dried for solvent, then use dichloromethane extraction, organic layer anhydrous magnesium sulfate drying, is spin-dried for, and then carries out column chromatography (PE), obtains weak yellow liquid 2.5g, productive rate 33.3%.
1HNMR(400MHz，CDCl 3)δ：7.22-6.70(m，13H)，3.92(s，4H)，1.81-1.72(m，4H)，1.49-1.41(m，4H)，1.38-1.30(m，16H)，0.93-0.88(m，6H).
In 100ml there-necked flask, add compound 4 (1.17g, 2.34mmol) and DMF (1.37g, 18.72mmol), under condition of ice bath, in flask, slowly drip (at least 30min) POCl 3(1.8g, 11.7mmol), after dropwising, under Ar protection, is warming up to rapidly 60 ℃ of stirring reaction 6h.After reaction finishes, reaction solution is slowly poured in frozen water, solution is neutralized to PH >=10 with sodium hydroxide, has immediately a large amount of dark red solid to separate out, and filters.Solid is dissolved in appropriate DCM, extracts 3 times.Organic layer is spin-dried for, and then puts into vacuum drying oven and is dried, and finally carries out column chromatography (PE: DCM=2: 1) obtain sticky shape yellow liquid 0.8g, productive rate 65%.
1H?NMR(400MHz，CDCl 3)δ：9.89(s，1H)，7.37(s，2H)，7.28(s，2H)，7.18(s，4H)，6.79(s，4H)，4.11(s，4H)，1.74(s，4H)，1.43(s，4H)，1.28(d，J＝20.0Hz，16H)，0.89(s，6H).
In 100ml there-necked flask, add compound 5 (530mg, 1mmol), compound 3 (165mg, 1mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, then use dichloromethane extraction 3 times, merge organic phase and with anhydrous magnesium sulfate drying, revolve to steam and obtain crude product except desolventizing, finally carry out column chromatography (EtOH/DCM=10: 1), obtain red solid 370mg, productive rate 76%.
1H?NMR(400MHz，DMSO)δ：8.04(s，2H)，7.40(s，1H)，7.32(s，2H)，7.16(s，4H)，6.77(s，4H)，4.10(s，4H)，1.74(s，4H)，1.43(s，4H)，1.28(d，J＝20.0Hz，16H)，0.89(s，6H).
HRMS (m/z): [M+H] +c 41h 49n 4o 3s theoretical value (CalCd for): 677.3525; Experimental value (Found): 677.3526.
Embodiment 3
In two mouthfuls of flasks of 100ml, add compound 4 (2.71g, 5.4mmol) and THF (40ml), under condition of ice bath, slowly add NBS (0.96g, 5.4mmol), remain at 0 ℃ and react 3h.After reaction finishes, revolve to steam and remove THF, then use dichloromethane extraction 3 times, collect organic phase and be spin-dried for solvent, then carry out column chromatography (PE), obtain colourless liquid 3g, productive rate 97%.
1H?NMR(400MHz，CDCl 3)：d＝7.22(d，J＝8.6Hz，2H)，7.00(d，J＝8.0Hz，4H)，6.81(d，J＝8.8Hz，4H)，6.78(d，J＝9.4Hz，2H)，3.92(t，J＝6.4Hz，4H)，1.77(m，4H)，1.45(m，4H)，1.34(m，16H)，0.91ppm(t，J＝7.0Hz，6H).
In two mouthfuls of flasks of 100ml, add compound 6 (390mg, 0.67mmol), Pd (PPh 3) 4(20mg, 0.017mmol), K 2cO 3(1.02g, 0.01mol) and 20mL THF, 5mL H 2o.After reflux 15min, inject 5-thiophenecarboxaldehyde-2-boric acid (105mg, 0.67mmol) that 5mL THF dissolves, reflux 12h.After reaction finishes, be cooled to room temperature, revolve to steam and remove organic solvent THF, crude product dichloromethane extraction 3 times, merge organic phase, anhydrous Na SO 4dry, revolve to steam and remove methylene dichloride, then carry out column chromatography (PE: DCM=1: 2).Obtain orange/yellow solid 190mg, productive rate 46.3%.
1H?NMR(400MHz，CDCl 3)δ：9.83(s，1H)，7.68(d，J＝4.0Hz，1H)，7.47-7.43(m，2H)，7.25(d，J＝4.0Hz，1H)，7.10-7.05(m，4H)，6.91-6.88(m，2H)，6.86-6.83(m，4H)，3.94(t，J＝6.5Hz，4H)，1.82-1.74(m，4H)，1.49-1.43(m，4H)，1.35-1.27(m，16H)，0.89(t，J＝6.9Hz，6H).
In 100ml there-necked flask, add compound 7 (170mg, 0.28mmol), compound 3 (46mg, 0.28mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, then use dichloromethane extraction 3 times, merge organic phase and with anhydrous magnesium sulfate drying, revolve to steam and obtain crude product except desolventizing, finally carry out column chromatography (EtOH/DCM=10: 1), obtain red solid 110mg, productive rate 51.9%.
1H?NMR(400MHz，DMSO)δ：8.19(s，1H)，7.85(s，1H)，7.64(s，1H)，7.37(s，2H)，7.18(s，4H)，6.99(s，2H)，6.79(s，4H)，4.11(s，4H)，1.74(s，4H)，1.43(s，4H)，1.28(d，J＝20.0Hz，16H)，0.89(t，6H).
HRMS (m/z): [M+H] +c 45h 51n 4o 3s 2theoretical value (Calcd for): 759.3403; Experimental value (Found): 759.3394.
Embodiment 4
In 100ml there-necked flask, add compound 6 (1.74g; 3mmol); the THF that adds 10ml heavily to steam under Ar protection; stirring reaction 30min at-78 ℃, then injects butyllithium (1.6M inTHF, 3ml; 4.8mmol); at 78 ℃, continue reaction 1h, then slowly inject the rear reaction 2h that continues of trimethyl borate (500mg, 4.8mmo).Reaction solution is risen to room temperature gradually and continue stirring reaction 2h.After reaction finishes, in reaction solution, drip 1M HCl until neutrality extracts, after organic phase is spin-dried for, do not do aftertreatment and directly throw next step.
In two mouthfuls of flasks of 100ml, add compound 4,7-bis-is bromo-2,1,3-diazosulfide (882mg, 3mmol), Pd (PPh 3) 4(20mg, 0.017mmol), K 2cO 3(1.02g, 0.01mol) and 20mLTHF, 5mL H 2o.After reflux 15min, inject the previous step products therefrom 8 that 5mL THF dissolves, reflux 12h.After reaction finishes, be cooled to room temperature, revolve to steam and remove organic solvent THF, crude product dichloromethane extraction 3 times, merge organic phase, anhydrous Na SO 4dry, revolve to steam and remove methylene dichloride, then carry out column chromatography (PE: DCM=3: 1).Obtain red solid 1.1g, productive rate 51.4%.
1H?NMR(400MHz，CDCl 3)δ：7.89(d，J＝7.6Hz，1H)，7.80-7.74(m，2H)，7.52(d，J＝7.7Hz，1H)，7.17-7.11(m，4H)，7.05(d，J＝8.8Hz，2H)，6.90-6.84(m，4H)，3.97(t，J＝6.5Hz，4H)，1.85-1.76(m，4H)，1.53-1.46(m，4H)，1.39-1.30(m，16H)，0.92(dd，J＝9.2，4.6Hz，6H).
In two mouthfuls of flasks of 100ml, add compound 9 (500mg, 0.7mmol), Pd (PPh 3) 4(20mg, 0.017mmol), K 2cO 3(1.02g, 0.01mol) and 20mL THF, 5mL H 2o.After reflux 15min, inject 5-thiophenecarboxaldehyde-2-boric acid (109mg, 0.7mmol) that 5mL THF dissolves, reflux 12h.After reaction finishes, be cooled to room temperature, revolve to steam and remove organic solvent THF, crude product dichloromethane extraction 3 times, merge organic phase, anhydrous Na 2sO 4dry, revolve to steam and remove methylene dichloride, then carry out column chromatography (PE: DCM=1: 2).Obtain red solid 390mg, productive rate 74.9%.
1H?NMR(400MHz，CDCl 3)δ：9.99(s，1H)，8.22(d，J＝4.0Hz，1H)，8.05(d，J＝7.6Hz，1H)，7.88-7.84(m，3H)，7.73(d，J＝7.6Hz，1H)，7.15(d，J＝8.0Hz，4H)，7.06(d，J＝8.2Hz，2H)，6.88(d，J＝8.9Hz，4H)，3.97(t，J＝6.5Hz，4H)，1.85-1.76(m，4H)，1.53-1.45(m，4H)，1.40-1.30(m，16H)，0.92(dd，J＝8.8，5.0Hz，6H).
In 100ml there-necked flask, add compound 10 (230mg, 0.31mmol), compd A (51mg, 0.31mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, then use dichloromethane extraction 3 times, merge organic phase and with anhydrous magnesium sulfate drying, revolve to steam and obtain crude product except desolventizing, finally carry out column chromatography (EtOH/DCM=10: 1), obtain red-purple solid 210mg, productive rate 76.1%.
1H?NMR(400MHz，DMSO)δ：8.19(s，1H)，7.85(s，1H)，7.68(d，J＝18.4Hz，2H)，7.64(s，1H)，7.55(s，2H)，7.37(s，2H)，7.19(d，J＝2.3Hz，1H)，7.18(s，4H)，6.79(s，4H)，4.11(s，4H)，1.74(s，4H)，1.43(s，4H)，1.28(d，J＝20.0Hz，16H)，0.89(s，6H).
HRMS (m/z): [M+H] +c45H51N4O3S2 theoretical value (Calcd for): 893.3341; Experimental value (Found): 893.3350.
Embodiment 5
In two mouthfuls of flasks of 50mL, add compound 7 (120mg, 0.20mmol), cyanoacetic acid (120mg, 1.40mmol), 50mg ammonium acetate and 15mL acetic acid, 120 ℃ of reaction 4h.Reaction finishes rear cooling, is poured into water, and filters and obtains crude product, puts into vacuum drying oven dry, then carries out column chromatography (CH 2cl 2-CH 2cl 2/ EtOH=10/1 (v/v)), obtain 90mg red solid, productive rate 67.2%.
1H?NMR(400MHz，DMSO)δ：8.34(s，1H)，7.87(d，J＝3.9Hz，1H)，7.53(dd，J＝13.3，6.3Hz，3H)，7.04(d，J＝8.8Hz，4H)，6.90(d，J＝8.9Hz，4H)，6.74(d，J＝8.8Hz，2H)，3.91(t，J＝6.3Hz，4H)，1.67(dd，J＝14.2，6.7Hz，4H)，1.38(d，J＝7.4Hz，4H)，1.26(d，J＝9.6Hz，16H)，0.85(dd，J＝8.7，4.5Hz，6H).
Embodiment 6
Compound I-1 of being prepared by embodiment 1～5 respectively, Compound I-2, Compound I-3, as depicted in figs. 1 and 2, its molar extinction coefficient and maximum absorption wavelength are in Table 1 for Compound I-4 and the Compound C A-1 uv-visible absorption spectra (Varian Cary 500) in dichloromethane solution and on titanium dioxide film.
Table 1
Embodiment 7
The test of the preparation and property of dye sensitization solar battery:
(1) preparation of dye sensitization solar battery:
A. clean conductive glass: FTO conductive glass is slit into 1.2 * 1.8cm, uses successively glass cleaner, clear water, acetone, intermediate water, washing with alcohol, dry up, stand-by.
B. platinized electrode: conductive glass surrounding is clung with adhesive plaster, conducting surface upward, at the aqueous isopropanol (20mM) of 2 Platinic chlorides of conductive glass spin coating, spin coating, after infrared lamp is dried, 400 ℃ are dried 15min, after cooling, make a call in position a hole, standby.
C. the preparation of dyestuff (Compound I-1～Compound I-5) solution: with methylene dichloride preparation 3 * 10 -4the dye solution of M.
D. the preparation of light anode: brush one deck TiO by silk screen printing on FTO conductive glass 2slurry, 125 ℃ are dried 6 minutes, cooling after, then be coated with one deck, 125 ℃ are dried 6min, are coated with altogether three layers, are then slowly warming up to 450 ℃ and dry 15min, then be warming up to 500 ℃ and dry 15min, are cooled to after room temperature, with the TiCl of 20mM 4aqueous solution room temperature treatment 12h, respectively by secondary washing, washing with alcohol, 450 ℃ are dried 30min, are steeped in dye solution (being prepared by step c) after cooling.After 12h, take out, with soaking the washing of dyestuff solvent for use, dry up.
E. electrolytical preparation: the acetonitrile of crossing with Non-aqueous processing and 2-methyl propionitrile are that the preparation of 9/1 mixed solvent contains 0.1M DMPII, 0.5M TBP, 0.05M I by volume 2solution with 0.15M LiI.
F. the encapsulation of battery: at the TiO that has adsorbed dyestuff 2heat curing-type rubber belt sealing circle sticks in the surrounding of film, to the conducting surface of electrode towards inner cap at TiO 2on film, aperture is in TiO 2the gap location of film and heat curing-type rubber belt sealing circle, with the encapsulation of battery packaging machine heating and pressurizing; In aperture, inject ionogen, vacuum is extracted the bubble of cell active area out, and ionogen is fully filled in the cavity of two electrodes, and finally sealed, makes dye sensitization solar battery.
(2) test of the performance of dye sensitization solar battery:
From light anode and the photocathode of above-mentioned battery, draw respectively wire respectively, receive on battery performance test device, the working area of battery is 0.25cm 2, use solar simulator simulated solar irradiation, light intensity is adjusted to 100mW/cm 2then the performance of test dye sensitization solar battery, as shown in Figure 3, photoelectric transformation efficiency is 3.46～7.04% to the battery discharge curve recording, short-circuit current is 8.63～13.64mAcm -2, open circuit voltage is 0.634～0.804V, packing factor is 0.63～0.72, refers to table 2:
Table 2
In table 2, we have contrasted the photovoltaic performance of Compound I-3 and CA-1, and because the absorption spectrum of Compound I-3 has obvious red shift compared with Compound C A-1, so its short-circuit current increases significantly compared with Compound C A-1.Although the open circuit voltage of Compound I-3 is a little less than Compound C A-1, the total photoelectric transformation efficiency in Compound I-3 is compared and has been improved 0.72% with Compound C A-1.This provides new direction for the research work of organic dye sensitized dose from now on.

Claims (4)

1. a Rhodanine derivates, its structure is suc as formula shown in I:
In formula I, A is group shown in formula II or formula III:
Wherein, R wherein 1and R 2independently be selected from respectively: C 8～C 20the alkoxyl group of straight or branched, R 3for C 8～C 20the alkyl of straight or branched, curve representation replaces position;
L is group shown in formula IV:
In formula IV, X is S or O, and n is 0 or 1, and curve representation replaces position;
M is 0 or 1.
2. Rhodanine derivates as claimed in claim 1, is characterized in that, wherein R 1and R 2be CH 3(CH 2) 7o-, R 3for n-octyl.
3. Rhodanine derivates as claimed in claim 1, is characterized in that, described Rhodanine derivates is formula I-1, formula I-2, and compound shown in formula I-3 or formula I-4:
4. the Rhodanine derivates as described in any one in claim 1～3 is as the application of the photosensitizers of dye sensitization solar battery.
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010074326A1 (en) * 2008-12-25 2010-07-01 Canon Kabushiki Kaisha Probe for a biological specimen and labelling method and screening method using the probe

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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CN102093740B (en) * 2011-01-21 2013-06-12 电子科技大学 Organic dye for dye sensitized solar cell and preparation method of organic dye

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010074326A1 (en) * 2008-12-25 2010-07-01 Canon Kabushiki Kaisha Probe for a biological specimen and labelling method and screening method using the probe

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
Alberto Insuasty，等.2-(1,1-dicyanomethylene) rhodanine: A novel, efficient electron acceptor.《Dyes and Pigments》.2010,第88卷(第3期),第385-390页. *
Braulio Insuasty，等.Synthesis and Antifungal Evaluation of Novel Dicyanoderivatives of Rhodanine.《Journal of Heterocyclic Chemistry》.2010,第48卷(第2期),第347-350页. *
JP特开2001-23705A 2001.01.26 *
JP特开2007-48680A 2007.02.22 *
Zhijun Ning，等.Triarylamine: a promising core unit for efficient photovoltaic materials.《Chem. Commun.》.2009,第45卷(第37期),第5483-5495页. *
田海宁.芳胺类光敏染料用于染料敏化太阳能电池的研究.《大连理工大学博士学位论文》.2009,第18、21-24、47-48页. *
芳胺类光敏染料用于染料敏化太阳能电池的研究;田海宁;《大连理工大学博士学位论文》;20090921;第18、21-24、47-48页 *

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