CN102532121A - Rhodanine derivative and application thereof - Google Patents
Rhodanine derivative and application thereof Download PDFInfo
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- CN102532121A CN102532121A CN2012100033580A CN201210003358A CN102532121A CN 102532121 A CN102532121 A CN 102532121A CN 2012100033580 A CN2012100033580 A CN 2012100033580A CN 201210003358 A CN201210003358 A CN 201210003358A CN 102532121 A CN102532121 A CN 102532121A
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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
Technical field
The present invention relates to a kind of rhodanine verivate and uses thereof, specifically, relate to a kind of based on propane dinitrile rhodanine verivate and uses thereof.
Background technology
Be accompanied by the develop rapidly of human industrial civilization and market economy, mineral Nonrenewable resources such as coal, oil and natural gas are exhausted day by day, and the energy dilemma and the environmental pollution that cause have thus become the globalization problem that needs to be resolved hurrily.Therefore people press for and seek other new alternative energy.Dye sensitization solar battery (B.O ' Regan; M.
Nature; 1991; 353,737-740), because of its have with low cost with make advantage potential practical values such as simple.
Dye sensitization solar battery (Dye-sensitized Solar Cells, DSSCs) common oxide semiconductor film (TiO by nanoporous
2), dye sensitizing agent, redox electrolytes matter (I
-/ I
3-) and counter electrode compositions such as (Pt), wherein be the core of whole DSSCs system to the transmission of the receptivity of sunshine and electronics.The best light-sensitive coloring agent of photoelectric transformation efficiency is bipyridyl ruthenium complex compound (about 12%) up to now, but owing to ruthenium costs an arm and a leg as rare metal, and the preparation process of dye sensitizing agent is complicated.Therefore, seek low-cost, be easy to prepare and base metal class organic photovoltaic cell sensitized material with applications well performance becomes the important content of current research.
Summary of the invention
Contriver of the present invention finds: (like (but being not limited to): the substituted triphen amido of triphen amido, alkyl or alkoxyl group, phenothiazinyl, the substituted phenothiazinyl of alkyl, carbazyl, substituted carbazyl, fluorenyl or replace fluorenyl etc.) is electron donor(ED) or/and the group of many cyclophanes heterocyclic radical to contain many cyclophanes cyclic group; With 2-(1 ', 1 '-dicyano) rhodanine is as electron acceptor(EA); Or to contain many cyclophanes cyclic group or/and the group of many cyclophanes heterocyclic radical is an electron donor(ED); With 2-(1 '; 1 '-dicyano) rhodanine is as electron acceptor(EA), is bridge chain base with the conjugation aromatic heterocyclic, the rhodanine verivate that is obtained; They all have unique photoelectrochemical behaviour, and can be adsorbed on the titanium oxide (TiO of nanoporous effectively
2) on the film, obtain higher photoelectric transformation efficiency.
In addition, the rhodanine verivate that provided of invention is easy to preparation and synthetic cost well below the bipyridyl ruthenium complex compound, can reduce the dye sensitization solar battery cost effectively.
Rhodanine verivate of the present invention, its structure is suc as formula shown in the I:
Among the 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 heterocyclic or substituted one or more aromatic heterocyclics; 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 the formula I, and promptly it can be used as the application of the photosensitizers of dye sensitization solar battery.
Description of drawings
Fig. 1 is that embodiment 1～5 prepared compound I-1～I-4 and the ultraviolet-visible of comparison CA-1 in methylene dichloride absorb spectrogram,
Wherein, what X-coordinate was represented is wavelength (unit is a nanometer), and what ordinate zou was represented is molar extinction coefficient (unit is for rising every mole every centimetre).
Fig. 2 is that compound I-1～I-4 and the ultraviolet-visible of comparison CA-1 on titanium dioxide film absorb spectrogram,
Wherein, what X-coordinate was represented is wavelength (unit is a nanometer), and what ordinate zou was represented is molar extinction coefficient (unit is for rising every mole every centimetre).
Fig. 3 is to be the I-V curve of the solar cell of photosensitizer with compound I-1～I-4 and comparison CA-1,
Wherein, what X-coordinate was represented is voltage (unit is volt), and what ordinate zou was represented is current density (unit is every square centimeter of milliampere).
Embodiment
In optimized technical scheme of the present invention, A is C
1～C
20The substituted triphenyl amido of the alkyl of straight or branched or alkoxyl group, or C
1～C
20The substituted phenothiazinyl of the alkyl of straight or branched or alkoxyl group;
In a preferred technical scheme, A is C
8～C
20The substituted triphenyl amido of the alkyl of straight or branched or alkoxyl group, or C
8～C
20The substituted phenothiazinyl of the alkyl of straight or branched or alkoxyl group;
In a further optimized technical scheme, A is a group shown in formula II or the 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 the alkoxyl group, curve representation replaces the 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
3Be C
8～C
20The alkyl of straight or branched;
Best R
1And R
2Be CH
3(CH
2)
7O-, best R
3Be n-octyl.
In another optimal technical scheme of the present invention, L is a group shown in the formula IV:
Among the formula IV, X is S or O, and n is 0 or 1, and curve representation replaces the position.
Or/and can making, strategy invents said rhodanine verivate (compound shown in the formula I) through following method:
(1) prepare the method that m among the formula I is a compound under 0, it comprises the steps:
(A) under the condition that rare gas element exists, rhodanine and propane dinitrile are placed absolute ethyl alcohol, and under reflux state, kept at least 12 hours; Stopped reaction is cooled to room temperature, revolves to steam to remove etoh solvent; Dichloromethane extraction three times; Merge organic phase and revolve driedly, carry out recrystallization with absolute ethyl alcohol then, intermediate A (compound shown in the 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 is of preamble) and the formula V is placed ethanol; And under reflux state, kept at least 6 hours, stopped reaction is cooled to room temperature; Revolve to steam and remove etoh solvent, dichloromethane extraction three times merges organic phase; Revolve to steam to remove and desolvate, carry out column chromatography then, obtain target compound (m is 0 affiliated compound among the formula I).
(2) m is that the strategy of compound is under 1 among the synthesis type I, at first by compd A-Br (definition of A is of preamble) or A '-Br (its structure is suc as formula shown in the VI) and the reaction of compound shown in the formula VII, obtains intermediate B (its structure is suc as formula shown in the VIII); Then by compound shown in compound shown in the formula VIII and formula V reaction, obtain target compound (m is a compound under 1 among the I), the concrete steps listed embodiment that vide infra.
Wherein, the implication of X, n and A is said identical with preamble.
With rhodanine verivate according to the invention (compound shown in the formula I) is that the dye sensitization solar battery of photosensitizers mainly is made up of light anode, photocathode and their substrate and ionogen; The material of light anode and photocathode substrate is a 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 are provided with, and periphery forms airtight cavity with the sealing material sealing, is filled with ionogen in the cavity.
A kind of method for preparing above-mentioned dye sensitization solar battery comprises the steps:
A. clean conductive glass: the FTO conductive glass is slit into 1.2 * 1.8cm, uses glass cleaner, clear water, acetone, secondary water, washing with alcohol successively, dry up, for use.
B. platinized electrode: cling with adhesive plaster around the conductive glass, conducting surface up, the aqueous isopropanol (2 * 10 of spin coating Platinic chloride on conductive glass
-4M), after the ir lamp oven dry, 400 ℃ of baking 15min after cooling, make a call to a hole in position, and are subsequent use.
C. the preparation of dyestuff (compound shown in the formula I) solution: with methylene dichloride preparation 3 * 10
-4The dye solution of M.
D. light anodic preparation: (0.5 * 0.5cm) brushes one deck TiO on the FTO conductive glass through silk screen printing
2Slurry, 125 ℃ the baking 6 minutes, after the cooling, be coated with one deck again, 125 ℃ the baking 6min, be coated with altogether two-layer, slowly be warming up to then 450 ℃ the baking 15min, be warming up to again 500 ℃ the baking 15min, be cooled to room temperature after, with the TiCl of 20mM
4Aqueous solution room temperature treatment 12h uses secondary water washing, washing with alcohol respectively, and 450 ℃ of baking 30min steep it in dye solution (promptly by step c preparation) after the cooling.Take out behind the 12h,, dry up with soaking the washing of dyestuff solvent for use.
E. electrolytical preparation: acetonitrile and the 2-methyl propionitrile that uses no water treatment is that 9/1 mixed solvent is prepared and contained 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
2Stick heat curing-type rubber belt sealing circle around the film, the conducting surface of counter electrode towards inner cap at TiO
2On the film, aperture is in TiO
2The gap location of film and heat curing-type rubber belt sealing circle encapsulates with battery packaging machine heating and pressurizing; In aperture, inject ionogen, vacuum is extracted the bubble of cell active area out, and ionogen fully is filled in the cavity of two electrodes, and finally sealed makes dye sensitization solar battery.
The test of above-mentioned dye sensitization solar battery:
Draw lead respectively from the light anode and the photocathode of tested battery, receive on the battery performance test device, the working area of battery is confirmed through the square hole splicing tape of a 0.5 * 0.5cm; With solar simulator (91160 types; Newport, USA) simulated solar irradiation, with light intensity regulating to 100mW/cm
2, the photoelectric transformation efficiency that records 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 (seeing embodiment 8 for details).
Propane dinitrile rhodanine verivate 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 present invention provides propane dinitrile rhodanine verivate to have synthetic simple, low cost and other advantages.
The present invention simultaneously is substituted with propane dinitrile rhodanine group first and uses very general cyanoacetic acid in the organic dye sensitizing agent as electron acceptor(EA); And itself and the compound that contains cyanoacetic acid compared, experiment finds to have higher photoelectric transformation efficiency based on the organic dye of propane dinitrile rhodanine.This provides new direction for organic dye sensitized dose research work from now on.
Below by embodiment the present invention is further elaborated, its purpose only is better to understand content of the present invention.Therefore, the example of being takeed does not limit protection scope of the present invention:
In the following example, said room temperature is meant 20 ℃～25 ℃, and used raw material and reagent are commercially available article.
Embodiment 1
In the 100ml there-necked flask, add rhodanine (2.66g, 20mmol), propane dinitrile (1.32g, 20mmol), sodium-acetate (1.64g, 20mmol) and absolute ethyl alcohol (60ml), reflux 12h under the Ar protection.After reaction finishes, revolve to steam and remove etoh solvent, remaining solid merges organic phase and removes methylene dichloride with revolving steaming behind the anhydrous magnesium sulfate drying with dichloromethane extraction 3 times, carries out recrystallization with absolute ethyl alcohol then, obtains 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.
(10g, 50mmol), (5g, 0.1mol) and DMSO (100ml), (1.6g, 5mmol), 30min is at room temperature stirred in reaction to 5g sodium hydroxide to add the 1.6g tetra-n-butyl ammonium bromide then in the 250ml there-necked flask, to add thiodiphenylamine.Slowly drip then (20min at least) 1-bromooctane (16.62g, 55mmol), stirring reaction 24h at room temperature.Reaction is poured reaction solution in the water into after finishing, and the limit bevelling stirs, dichloromethane extraction 3 times, and extraction liquid is used anhydrous MgSO
4Drying is revolved driedly, carries out column chromatography (PE) then.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 the 100ml there-necked flask, add compound 1 (3.11g, 10mmol) with DMF (3.65g, 0.05mol), under the condition of ice bath in flask slow dropping (30min at least) POCl
3(7.68g 0.05mol), after dropwising, under the Ar protection, is warming up to 90 ℃ of stirring reaction 6h rapidly.Reaction is slowly poured reaction solution in the frozen water after finishing, and solution is neutralized to PH >=10 with sodium hydroxide, has a large amount of dark red solid to separate out immediately, filters.Solid is dissolved among an amount of DCM, extracts 3 times.Organic layer revolves dried, puts into vacuum drying oven then and carries out drying, carries out column chromatography (PE: DCM=3: 1) obtain sticky shape yellow liquid 1.46g, productive rate 43% at last.
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).
Adding compound 2 in the 100ml there-necked flask (339mg, 1mmol), compd A (165mg, 1mmol), 5% aqueous sodium hydroxide solution (0.3mI).Under the Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, use dichloromethane extraction then 3 times; Merge organic phase and use anhydrous magnesium sulfate drying, revolve steaming except that desolvating and obtain crude product, carry out column chromatography (EtOH/DCM=10: 1) at last; 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).
In the 250ml there-necked flask, add to iodophenol (8.8g, 40mmol), the 1-bromooctane (8ml, 44mmol), salt of wormwood (10.04g, 80mmol) and potassiumiodide (6g, 40mmol).Under the Ar protection, add 80ml DMF, be warming up to 90 ℃ of stirring reaction 24h.After reaction finishes, reaction solution poured into be stirred to ice in the frozen water and melt CH fully
2Cl
2Extraction, washing, organic phase has anhydrous sodium sulfate drying, revolves dried solvent, carries out column chromatography (PE) then.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 the 250ml there-necked flask, add pentanoic (1.4g, 15mmol), 3 (25.2g, 76mmol), phenanthroline (2.97g, 15mmol), cuprous chloride (2.87g, 15mmol), Pottasium Hydroxide (3.36g, 60mmol), toluene (80ml).At Ar protection refluxed reaction 48h.After reaction finishes, revolve dried solvent, use dichloromethane extraction then, organic layer is used anhydrous magnesium sulfate drying, revolves driedly, carries out column chromatography (PE) then, 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 the 100ml there-necked flask, add compound 4 (1.17g, 2.34mmol) with DMF (1.37g, 18.72mmol), under the condition of ice bath in flask slow dropping (30min at least) POCl
3(1.8g 11.7mmol), after dropwising, under the Ar protection, is warming up to 60 ℃ of stirring reaction 6h rapidly.Reaction is slowly poured reaction solution in the frozen water after finishing, and solution is neutralized to PH >=10 with sodium hydroxide, has a large amount of dark red solid to separate out immediately, filters.Solid is dissolved among an amount of DCM, extracts 3 times.Organic layer revolves dried, puts into vacuum drying oven then and carries out drying, carries out column chromatography (PE: DCM=2: 1) obtain sticky shape yellow liquid 0.8g, productive rate 65% at last.
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).
Adding compound 5 in the 100ml there-necked flask (530mg, 1mmol), compound 3 (165mg, 1mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under the Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, use dichloromethane extraction then 3 times; Merge organic phase and use anhydrous magnesium sulfate drying, revolve steaming except that desolvating and obtain crude product, carry out column chromatography (EtOH/DCM=10: 1) at last; 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.
(2.71g, 5.4mmol) with THF (40ml), (0.96g 5.4mmol), remains on 0 ℃ and reacts 3h down slowly to add NBS under the condition of ice bath in two mouthfuls of flasks of 100ml, to add compound 4.After reaction finishes, revolve to steam and remove THF, use dichloromethane extraction then 3 times, collect organic phase and revolve dried solvent, carry out column chromatography (PE) then, 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).
Adding compound 6 in two mouthfuls of flasks of 100ml (390mg, 0.67mmol), Pd (PPh
3)
4(20mg, 0.017mmol), K
2CO
3(1.02g, 0.01mol) with 20mL THF, 5mL H
2O.Behind the reflux 15min, and injection 5mL THF dissolved 5-thiophenecarboxaldehyde-2-boric acid (105mg, 0.67mmol), reflux 12h.Reaction finishes postcooling to room temperature, revolves to steam to remove organic solvent THF, and crude product is with dichloromethane extraction 3 times, merging organic phase, anhydrous Na SO
4Drying is revolved to steam and is removed methylene dichloride, carries out column chromatography (PE: DCM=1: 2) then.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).
Adding compound 7 in the 100ml there-necked flask (170mg, 0.28mmol), compound 3 (46mg, 0.28mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under the Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, use dichloromethane extraction then 3 times; Merge organic phase and use anhydrous magnesium sulfate drying, revolve steaming except that desolvating and obtain crude product, carry out column chromatography (EtOH/DCM=10: 1) at last; 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
(1.74g 3mmol), adds the THF that 10ml heavily steams under the Ar protection in the 100ml there-necked flask, to add compound 6;-78 ℃ of following stirring reaction 30min inject butyllithium (1.6M inTHF, 3ml then; 4.8mmol); Continue reaction 1h down at 78 ℃, slowly inject trimethyl borate (500mg, 4.8mmo) continued reaction 2h then.Reaction solution is risen to room temperature gradually continue stirring reaction 2h.After reaction finishes, in reaction solution, drip 1M HCl until neutrality, extraction is not done aftertreatment after organic phase is revolved and done and is directly thrown next step.
In two mouthfuls of flasks of 100ml, add compound 4,7-two bromo-2,1, the 3-diazosulfide (882mg, 3mmol), Pd (PPh
3)
4(20mg, 0.017mmol), K
2CO
3(1.02g, 0.01mol) and 20mLTHF, 5mL H
2O.Behind the reflux 15min, inject a step products therefrom 8 on the 5mL THF dissolved, reflux 12h.Reaction finishes postcooling to room temperature, revolves to steam to remove organic solvent THF, and crude product is with dichloromethane extraction 3 times, merging organic phase, anhydrous Na SO
4Drying is revolved to steam and is removed methylene dichloride, carries out column chromatography (PE: DCM=3: 1) then.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).
Adding compound 9 in two mouthfuls of flasks of 100ml (500mg, 0.7mmol), Pd (PPh
3)
4(20mg, 0.017mmol), K
2CO
3(1.02g, 0.01mol) with 20mL THF, 5mL H
2O.Behind the reflux 15min, and injection 5mL THF dissolved 5-thiophenecarboxaldehyde-2-boric acid (109mg, 0.7mmol), reflux 12h.Reaction finishes postcooling to room temperature, revolves to steam to remove organic solvent THF, and crude product is with dichloromethane extraction 3 times, merging organic phase, anhydrous Na
2SO
4Drying is revolved to steam and is removed methylene dichloride, carries out column chromatography (PE: DCM=1: 2) then.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).
Adding compound 10 in the 100ml there-necked flask (230mg, 0.31mmol), compd A (51mg, 0.31mmol), 5% aqueous sodium hydroxide solution (0.3ml).Under the Ar protection, add 20ml ethanol, heating reflux reaction 12h.After reaction finishes, revolve to steam and remove etoh solvent, use dichloromethane extraction then 3 times; Merge organic phase and use anhydrous magnesium sulfate drying, revolve steaming except that desolvating and obtain crude product, carry out column chromatography (EtOH/DCM=10: 1) at last; 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 acetate, 120 ℃ of reaction 4h.Reaction finishes postcooling, pours in the water, filters and obtains crude product, and it is dry to put into vacuum drying oven, carries out column chromatography (CH then
2Cl
2-CH
2Cl
2/ EtOH=10/1 (v/v)), obtains the 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).
The compound I-1 for preparing by embodiment 1～5 respectively; Compound I-2; Compound I-3; Compound I-4 and the Compound C A-1 uv-visible absorption spectra (Varian Cary 500) in dichloromethane solution and on the titanium dioxide film is as depicted in figs. 1 and 2, and its molar extinction coefficient and maximum absorption wavelength are seen table 1.
Table 1
Embodiment 7
The preparation of dye sensitization solar battery and the test of performance:
(1) preparation of dye sensitization solar battery:
A. clean conductive glass: the FTO conductive glass is slit into 1.2 * 1.8cm, uses glass cleaner, clear water, acetone, secondary water, washing with alcohol successively, dry up, for use.
B. platinized electrode: cling with adhesive plaster around the conductive glass, conducting surface up, at the aqueous isopropanol (20mM) of 2 Platinic chlorides of conductive glass spin coating, spin coating, after the ir lamp oven dry, 400 ℃ of baking 15min after cooling, make a call to a hole in position, and are subsequent use.
C. the preparation of dyestuff (compound I-1～compound I-5) solution: with methylene dichloride preparation 3 * 10
-4The dye solution of M.
D. light anodic preparation: on the FTO conductive glass, brush one deck TiO through silk screen printing
2Slurry, 125 ℃ the baking 6 minutes, after the cooling, be coated with one deck again, 125 ℃ the baking 6min, be coated with three layers altogether, slowly be warming up to then 450 ℃ the baking 15min, be warming up to again 500 ℃ the baking 15min, be cooled to room temperature after, with the TiCl of 20mM
4Aqueous solution room temperature treatment 12h uses secondary water washing, washing with alcohol respectively, and 450 ℃ of baking 30min steep it in dye solution (promptly by step c preparation) after the cooling.Take out behind the 12h,, dry up with soaking the washing of dyestuff solvent for use.
E. electrolytical preparation: acetonitrile and the 2-methyl propionitrile that uses no water treatment is that 9/1 mixed solvent is prepared and contained 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
2Stick heat curing-type rubber belt sealing circle around the film, the conducting surface of counter electrode towards inner cap at TiO
2On the film, aperture is in TiO
2The gap location of film and heat curing-type rubber belt sealing circle encapsulates with battery packaging machine heating and pressurizing; In aperture, inject ionogen, vacuum is extracted the bubble of cell active area out, and ionogen fully is 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:
Draw lead respectively from the light anode and the photocathode of above-mentioned battery respectively, receive on the battery performance test device, the working area of battery is 0.25cm
2, use the solar simulator simulated solar irradiation, light intensity is adjusted to 100mW/cm
2The performance of test dye sensitization solar battery then, the battery discharge curve that records is as shown in Figure 3, and photoelectric transformation efficiency is 3.46～7.04%, and short-circuit current is 8.63～13.64mAcm
-2, open circuit voltage is 0.634～0.804V, packing factor is 0.63～0.72, sees table 2 for details:
Table 2
We have contrasted the photovoltaic performance of compound I-3 and CA-1 in table 2, because the absorption spectrum of compound I-3 has tangible red shift than Compound C A-1, so its short-circuit current increases significantly than Compound C A-1.Though the open circuit voltage of compound I-3 is a little less than Compound C A-1, the total photoelectric transformation efficiency of compound I-3 is compared with Compound C A-1 and has been improved 0.72%.This provides new direction for organic dye sensitized dose research work from now on.
Claims (9)
1. rhodanine verivate, its structure is suc as formula shown in the l:
Among the 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 heterocyclic or substituted one or more aromatic heterocyclics; L is one or more conjugation aromatic heterocyclic of divalence; M is 0 or 1.
2. rhodanine verivate as claimed in claim 1 is characterized in that, wherein A is C
1～C
20The substituted triphenyl amido of the alkyl of straight or branched or alkoxyl group, or C
1～C
20The substituted phenothiazinyl of the alkyl of straight or branched or alkoxyl group.
3. rhodanine verivate as claimed in claim 2 is characterized in that, wherein A is C
8～C
20The substituted triphenyl amido of the alkyl of straight or branched or alkoxyl group, or C
8～C
20The substituted phenothiazinyl of the alkyl of straight or branched or alkoxyl group.
4. rhodanine verivate as claimed in claim 3 is characterized in that, wherein A is a group shown in formula II or the 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 the alkoxyl group, curve representation replaces the position.
5. rhodanine verivate as claimed in claim 4 is characterized in that, wherein R
1And R
2Independently be selected from respectively: C
8～C
20A kind of in the alkoxyl group of straight or branched, R
3Be C
8～C
20The alkyl of straight or branched.
6. rhodanine verivate as claimed in claim 5 is characterized in that, wherein R
1And R
2Be CH
3(CH
2)
7O-, R
3Be n-octyl.
7. like any described rhodanine verivate in the claim 1～6, it is characterized in that L is a group shown in the formula IV:
Among the formula IV, X is S or O, and n is 0 or 1, and curve representation replaces the position.
8. rhodanine verivate as claimed in claim 7 is characterized in that, described rhodanine verivate is formula I-1, formula I-2, and compound shown in formula I-3 or the formula I-4:
。
Like any described rhodanine verivate in the claim 1～8 as the application of the photosensitizers of dye sensitization solar battery.
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| CN103450700A (en) * | 2013-08-23 | 2013-12-18 | 中山大学 | Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell |
| CN103788679A (en) * | 2014-01-24 | 2014-05-14 | 华南理工大学 | Double-strand phenothiazine dye with benzotriazole led into Pi bridge and application thereof in preparation of dye-sensitized solar cells |
| CN104262321A (en) * | 2014-09-17 | 2015-01-07 | 山东盛华电子新材料有限公司 | Novel solar dye sensitized compound as well as preparation method and application of novel solar dye sensitized compound |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103073541A (en) * | 2013-01-07 | 2013-05-01 | 中国科学院宁波材料技术与工程研究所 | Triphenylamine star-shaped material modified by electron withdrawing group, preparation method and application thereof |
| CN103450700A (en) * | 2013-08-23 | 2013-12-18 | 中山大学 | Tree-based organic dyestuff based on carbazole or triphenylamine derivatives and application thereof in preparation of dye-sensitized solar cell |
| CN103450700B (en) * | 2013-08-23 | 2015-12-02 | 中山大学 | A kind of tree-shaped organic dye based on carbazole or triphenylamine derivative and preparing the application in dye sensitization solar battery |
| CN103788679A (en) * | 2014-01-24 | 2014-05-14 | 华南理工大学 | Double-strand phenothiazine dye with benzotriazole led into Pi bridge and application thereof in preparation of dye-sensitized solar cells |
| CN103788679B (en) * | 2014-01-24 | 2015-09-16 | 华南理工大学 | In π bridge, introduce the double-strand phenothiazine dyes of benzotriazole and preparing the application in dye-sensitized solar cells |
| CN104262321A (en) * | 2014-09-17 | 2015-01-07 | 山东盛华电子新材料有限公司 | Novel solar dye sensitized compound as well as preparation method and application of novel solar dye sensitized compound |
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