CN103087051A - Synthesis and application of coumarin type dye sensitizer - Google Patents

Synthesis and application of coumarin type dye sensitizer Download PDF

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CN103087051A
CN103087051A CN2013100171053A CN201310017105A CN103087051A CN 103087051 A CN103087051 A CN 103087051A CN 2013100171053 A CN2013100171053 A CN 2013100171053A CN 201310017105 A CN201310017105 A CN 201310017105A CN 103087051 A CN103087051 A CN 103087051A
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formula
dye
coumarin
compound
thiophene
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韩亮
叶青
李郁锦
高建荣
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Zhejiang University of Technology ZJUT
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Abstract

The invention relates to a coumarin functional dye containing a thiophene bridge chain in the field of fine chemical industry and organic photoelectric material applications. The structure of the coumarin functional dye takes coumarin and a derivative thereof as an electron donor, contains a thiophene structure unit capable of adjusting an absorption spectrum and a fluorescence emission spectrum as the bridge chain and is further connected with a cyanoacetic acid electron withdrawing group. Coumarin-thiophene, POCl3/DMF (dimethyl fumarate) are added into a reaction container by adopting general reaction for reaction so as to get a 5-(7-substiutted-2-carbonyl-2H-benzopyran-3-yl) thiophene-2-formaldehyde intermediate (II) with an aldehyde group; and the intermediate II with the aldehyde group further reacts with cyanoacetic acid to get the coumarin dye connected by the thiophene. As the coumarin is taken as a chromophore, the electron donating capability is good; the thiophene has high electron cloud density and special optical properties and electron transmission capability; and the electron withdrawing group of the cyanoacetic acid is further connected for enabling the dye to have good light, thermal and chemical stability and photoelectric properties. Therefore, the dye can be used as a photosensitive dye for dye-sensitized solar cells.

Description

A kind of synthetic and application of coumarin type dye sensitizing agent
(1) technical field
The present invention relates to the synthetic of a kind of coumarin type dye sensitizing agent and use.
(2) background technology
Dye sensitization solar battery (Dye Sensitized Solar Cell, DSSC) but rely on the not characteristics such as temperature influence of the low low light level Generate, Generation, Generator electricity of its cost transformation efficiency, the utmost point is hopeful substituted for silicon semiconductor optoelectronic converting member, becomes practical high performance solar cells of future generation.Dye sensitizing agent is the key structure material that determines visible absorption and photoelectric transformation efficiency in DSSC, has structure and easily designs the characteristics such as modification and processing, cost are low, good stability.
The research of Chinese and foreign dyes sensitizing agent at present mainly divides two classes, and a class is organometallic complex, and typical structure is functional many pyridines ruthenium compound.This class dye sensitizing agent absorbs stronger at visible region, redox property is reversible, and oxidative stability is high, but ruthenium is higher as the rare metal cost, and its dyestuff absorption spectrum is narrow.Equations of The Second Kind is nonmetal organic dye, has that molar absorptivity is high, an absorb light spectrum width and can produce by the structural modification modulation advantage such as good electric chemical property, is the study hotspot of dye sensitizing agent in recent years.
Tonka bean camphor and derivative thereof have good fluorescence quantum efficiency, high molar absorptivity and large Stoke displacement, be widely used in the color fluorescence resin of coloring plastic, color fluorescence coating, solar collector, and the high-technology field such as sensitive materials, photochromics, video disc recording material.Due to high in the visible region responsive, the solar light irradiation stability inferior is good, the coumarins dye molecule has been subject to extensive concern as a good dye sensitizing agent of class development prospect.A series of coumarins dye sensitization agent molecules have been synthesized in the designs such as Hara, and photoelectric transformation efficiency is up to 8.2%; Recently Kim etc. has reported that total efficiency is 5.97% take tonka bean camphor as to the novel D-A-π of body-category-A amboceptor coumarine dye sensitizing agent molecule; Design in great waves that to have synthesized novel 2D-π-category-A two to body note legumin dye sensitization agent molecule, its photoelectric transformation efficiency has reached 5.53%.These coumarine dye sensitizing agent molecules generally use a pair of horses going side by side two nitrogenous heterocyclic tonka bean camphors conducts to be arranged to body, and its synthesis step is longer, and yield is not high.The substituted cumarin that the present invention is easy to get with raw material is as giving body, and thiophene is as bridged bond, and cyanoacetic acid is as acceptor, synthesize and obtained two coumarins dye sensitization agent molecules simple in structure, and its photoelectric properties are studied, at present, there is no the solar cell application of this structure of bibliographical information.
(3) summary of the invention
The object of the present invention is to provide preparation of a kind of coumarin kind compound and uses thereof, the present invention has excellent chemical property.
Structural formula of the present invention is as follows:
Figure 2013100171053100002DEST_PATH_IMAGE001
I
In formula I, R is N, N-dimethyl, methoxyl group.
The present invention also provides the preparation method of the compound shown in formula I:
Formula (II) compound and formula III compound are mixed with organic solvent A, under the effect of alkaline matter B, the reflux stirring reaction, TLC follows the tracks of reaction, after reacting completely, separate out solid, filter, filter cake carries out silica gel column chromatography or carries out recrystallization with recrystallization solvent, the coumarin kind compound shown in acquisition formula (I); Described organic solvent A is acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or acetone, preferred acetonitrile; Described alkaline matter is piperidines, pyridine, triethylamine or dimethylamine, is preferably piperidines; The ratio of the amount of substance of described formula (II) compound and formula (III) compound and alkaline matter is 1:1.0 ~ 3.0:0.1 ~ 1.0, and the organic solvent volumetric usage is counted 2-20 mL/mmol. with the amount of substance of formula (II) compound
Figure 249478DEST_PATH_IMAGE002
In formula II, R is N, N-dimethyl, methoxyl group.
The reaction equation of described reaction is:
Figure 2013100171053100002DEST_PATH_IMAGE003
In described method, described reaction solution method for separating and processing is: after reaction finished, reaction solution was spin-dried for, and obtains product III with Gossypol recrystallized from chloroform.
The consumption of described organic solvent A is counted 2 ~ 20 mL/mmol with the amount of substance shown in formula II, preferred 15 mL/mmol.
The consumption of described alkaline matter is counted 0.1 ~ 1mL/mmol with the amount of substance of II, preferred 0.25 mL/mmol.
Comparatively concrete, the preparation method of the coumarin kind compound shown in described formula I carries out according to the following steps:
Formula (II) compound and formula III compound are mixed with organic solvent A, under the effect of alkaline matter B, the reflux stirring reaction, TLC follows the tracks of reaction, after reacting completely, separate out solid, filter, filter cake carries out silica gel column chromatography or carries out recrystallization with recrystallization solvent, the coumarin kind compound shown in acquisition formula (I); Described organic solvent A is acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or acetone; Described alkaline matter is piperidines, pyridine, triethylamine or dimethylamine; The ratio of the amount of substance of described formula (II) compound and formula (III) compound and alkaline matter is 1:1.0 ~ 3.0:0.1 ~ 1.0, and the organic solvent volumetric usage is counted 2-20 mL/mmol. with the amount of substance of formula (II) compound
In the inventive method, the tonka bean camphor thiophene aldehyde compound shown in formula II can prepare by the following method: substituted thiophene basic note legumin intermediate VI and DMF/POCl 3Reaction under the temperature that is fit to, solvent and certain molar ratio and preparation, this is to well known to a person skilled in the art the preparation method.
Figure 41984DEST_PATH_IMAGE004
VI
Coumarin kind compound shown in formula I of the present invention can be used as the dyestuff photosensitizers, and is concrete, and described coumarin kind compound can be used as bright solar cell.
Substantive distinguishing features of the present invention can be achieved from following examples of implementation, but these examples of implementation only as an illustration, rather than limits the invention.
  
Description of drawings
Fig. 1 is the coumarins dye sensitizing agent of embodiment IIIAt acetonitrile-DMSO solution (V CH3CN: V DMSO=24:1) uv-visible absorption spectra
Fig. 2 is the coumarins dye sensitizing agent of embodiment III existsTiO 2The uv-visible absorption spectra of electrode
Fig. 3 be embodiment based on the coumarins dye sensitizing agent IIIThe bode figure of solar cell
Fig. 4 be embodiment based on the coumarins dye sensitizing agent IIIThe Nyquist figure of solar cell
Fig. 5 is the coumarine dye sensitizing agent of embodiment IIIThe IPCE curve
Fig. 6 is the coumarine dye sensitizing agent of embodiment IIIElectric current J- VCurve
Specific implementation method
Example 1:5-(7-N, N-dimethyl-2-carbonyl-2H-chromene-3-yl) thiophene-2-formaldehyde ( IIa) synthetic
Under ice bath and drying conditions, with POCl 3(2 mL) dropwise adds in DMF (2 mL), stirs half an hour, obtains Vilsmier reagent.With 7-N, N-dimethyl-3-(2 '-thienyl)-tonka bean camphor (5 mmol) is dissolved in DMF (15 mL), adds Vilsmier reagent, reaction 8 h under 60 oC.Cooling, reaction solution is poured in frozen water (30 mL), regulate pH=7 with the NaOH aqueous solution of 10 %, separate out a large amount of precipitations.Suction filtration, water (30 mL * 5) washing, then use a large amount of washing with alcohol, obtain the yellowish brown solid after drying. IIa: yield 82.4 %. fusing point 185 ~ 186 oC.
Example 2:5-(7-methoxyl group-2-carbonyl-2H-chromene-3-yl) thiophene-2-formaldehyde ( IIb) synthetic
Under ice bath and drying conditions, with POCl 3(2 mL) dropwise adds in DMF (2 mL), stirs half an hour, obtains Vilsmier reagent.7-methoxyl group-3-(2 '-thienyl)-tonka bean camphor (5 mmol) is dissolved in DMF (15 mL), adds Vilsmier reagent, reaction 8 h under 60 oC.Cooling, reaction solution is poured in frozen water (30 mL), regulate pH=7 with the NaOH aqueous solution of 10 %, separate out a large amount of precipitations.Suction filtration, water (30 mL * 5) washing, then use a large amount of washing with alcohol, obtain the yellowish brown solid after drying. IIb: yield 84.9%. fusing point 164 ~ 165 oC.
Example 3:2-cyano group-3-(5-(7-N, N-dimethyl-2-carbonyl-2H-chromene-3-yl) thiophene-2-yl) vinylformic acid IIIa's is synthetic
Will II a(2 mmol) and cyanoacetic acid (4 mmol) are dissolved in acetonitrile (30 mL), then add piperidines (0.5 mL), reflux 6 h.Cooling, suction filtration is with acetonitrile (20 mL * 3) washing.Drying, CHCl 3Recrystallization obtains the garnet solid. IIIa: yield 87.3 %. fusing point 282 ~ 283 oC; 1H NMR (500 MHz, DMSO) δ: 8.67 (s, 1H, C H=CCN), 8.43 (s, 1H, coumarin-4- H), 7.98 (d, J=4.3 Hz, 1H, thiophene- H), 7.86 (d, J=4.2 Hz, 1H, thiophene- H), 7.57 (d, J=9.0 Hz, 1H, Ar H), 6.83 (dd, J=9.0,2.3 Hz, 1H, Ar H), 6.65 (d, J=2.23 Hz, 1H, Ar H), 3.50 (q, J=7.0 Hz, 4H, C H 2CH 3), 1.16 (t, J=7.0 Hz, 6H, CH 2C H 3); HR-ESI-MS for C 21H 17N 2O 4S:Found:393.0927 [M-H] -; Calcd. 393.0909.
Example 4:2-cyano group-3-(5-(7-methoxyl group-2-carbonyl-2H-chromene-3-yl) thiophene-2-yl) vinylformic acid IIIb's is synthetic
Will II b(2 mmol) and cyanoacetic acid (4 mmol) are dissolved in acetonitrile (30 mL), then add piperidines (0.5 mL), reflux 6 h.Cooling, suction filtration is with acetonitrile (20 mL * 3) washing.Drying, CHCl 3Recrystallization obtains the garnet solid. IIIb: yield 75.6%. fusing point〉300 oC; 1H NMR (500 MHz, DMSO): δ 8.83 (s, 1H, C H=CCN), 8.45 (s, 1H, coumarin-4- H), 8.01 ~ 7.97 (m, 2H, thiophene- H), 7.77 (d, J=8.7 Hz, 1H, Ar H), 7.15 (s, 1H, Ar H), 7.07 (d, J=8.7,1H, Ar H), 3.91 (s, 3H, OC H 3); HR-ESI-MS for C 18H 10NO 5S:Found:352.0293 [M-H] -; Calcd. 352.0280.
The spectral quality test of example 5 dye sensitizing agents
Dye sensitizing agent is at acetonitrile-DMSO solution and TiO 2Uv-visible absorption spectra on electrode has reacted dyestuff in solution and has loaded to TiO 2On film to the receptivity of sunlight.
By accompanying drawing 1 and accompanying drawing 2, reflected dyestuff in solution and loaded to TiO 2On film to the receptivity of sunlight.By table 1, IIIbMaximum absorption band appear at 428 nm places, molar absorptivity is 4.2 * 10 4mol -1Lcm -1, and IIIaMaximum absorption band generation red shift, appear at 496 nm places.Dye sensitizing agent IIIaWith IIIbAt TiO 2Ultra-violet absorption spectrum maximum absorption band on film is 384 nm and 389 nm; Dyestuff is by carboxyl and TiO 2Absorption, IIIaWith IIIbMaximum emission wavelength lay respectively at 600 nm and 499 nm.
Table 1The coumarins dye sensitizing agent IIIOptical property
Figure 3
aAt CH 3CN-DMSO solvent (V CH3CN: V DMSO=maximum absorption wavelength λ the max and the molar absorptivity λ max that record in 24:1); bTiO in sensitivity 2Maximum absorption wavelength λ max on electrode; cAt CH 3CN-DMSO solvent (V CH3CN: V DMSO=the maximum emission wavelength that 24:1) records.
The electrochemical properties test of example 6 dye sensitizing agents
Can understand the molecular energy level structure by cyclic voltammetry, with the size of the value of estimation highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO).We adopt the cyclic voltammetry curve of dye solution by U.S. PAR EG﹠amp; The M283 of G company potentiostat is measured, and adopts three-electrode system, and glass-carbon electrode is working electrode, and platinum plate electrode is supporting electrode, Ag/AgNO 3Electrode is reference electrode; Electrolytic solution is the acetonitrile solution of 0.1 mol/L TBAP.
Measured the coumarins dye sensitizing agent at TiO 2Cyclic voltammetry curve on electrode, the HOMO energy level is by the first redox potential E of cyclic voltammetry curve oxObtain.Resulting redox potential E in experiment pData are with respect to Ag/Ag +Reference electrode, it is scaled current potential with respect to standard hydrogen electrode (NHE) so that comparison, i.e. E ox=E p+ 0.197 V.Lumo energy is by E LUMO=E ox-E 0-0Calculate.Wherein molecular transition can (E 0-0) by E 0-0=1240/λ intTry to achieve λ intBe the wavelength of normalized dyestuff absorption spectrum and fluorescence emission spectrum intersection, data are listed in Table 2Can find out the E of coumarins dye sensitizing agent LUMOBe the excited state current potential, compare TiO 2Conduction level (0.5 V vs. NHE) to bear, show that dyestuff excites rear electronic energy to inject smoothly TiO 2Generation current in conduction band, and its E HOMOThan ionogen I 2/ I -The right energy level (0.4 V vs. NHE) of electricity will just, show that the excited state dyestuff injects electronics to TiO 2After conduction band, the oxidation state dyestuff of formation can be from I on thermodynamics -Accept electronics and be reduced, complete current cycle.
Table 2The coumarins dye sensitizing agent IIIElectrochemical properties
Figure 4
aThe point of crossing of normalization method absorption spectrum and emmission spectrum; bOxidation potential Eox is in CH 3Obtain with the cyclic voltammetry test in CN-DMSO, be used for representing ground state energy HOMO; cE 0-0By E 0-0=1240/λ intCalculate; dE LUMOBy E ox-E 0-0Calculate.
Example 7 electrochemical impedance tests
EIS adopts the PARSTAT2273 electrochemical workstation of U.S. Pu Sidun company to measure, bias voltage-0.6 V.Attached Fig. 3 and accompanying drawing 4Nyquist figure and the Bode figure of the electrochemical impedance of coumarine dye sensitizing agent have been listed.Can find out from two figure, IIIaResistance corresponding to charge recombination has obvious enhancing.
The preparation of example 8 dye-sensitized nano electrodes and the assembling of battery device
Utilize the double-deck TiO of silk screen printing preparation 2Film of nanoparticles is as optoelectronic pole: the TiO of 20 nm that at first seal one deck 12 μ m are thick on conductive glass FTO 2Particle (DHS-TPP3, Dalian HeptaChroma SolarTech Co., Ltd.), calcining 30 min in retort furnace under 450 oC.Before contaminating material, burned film is immersed 0.04 molL -1TiCl 4Then the aqueous solution 70 oC pre-treatment 30 min distinguish water and alcohol flushing, and hair dryer dries up.After again calcining 30 min under retort furnace 450 oC, immerse 3 * 10 after being cooled to 80 oC -4MolL -1The acetonitrile of dyestuff and the 24 h sensitizations of DMSO solution room temperature.Preparation to electrode: adopt method for printing screen, with certain density H 2PtCl 6Solution is printed on the FTO conductive glass, then 400 oC retort furnace sintering 20 min.The TiO of absorbing dye 2Electrode becomes sandwich structure with platinum to electrode assembling, and is middle through thick ionomer Surlyn 1702 (DuPont) the heat-seal adhesive washer sealing of 60 μ m.TiO 2The area of electrode is 0.36 cm -2(i.e. 6 mm * 6 mm).To the aperture place's dropping electrolytic solution (DHS-E23 type, Dalian HeptaChroma SolarTech Co., Ltd.) on electrode, utilize the vacuum backfill technology to introduce inside battery.Aperture to electrode utilizes the sealing after heating of Surlyn 1702 and the thin glass of a fritter (0.1 mm is thick).
The opto-electronic conversion performance test of embodiment 9 dye sensitizing agents
Photoelectric transformation efficiency IPCE under monochromatic ray uses SM25 spectrophotometer (Japanese JASCO company) to measure.The test of photovoltage-current characteristics curve is to utilize LK 98BII type electrochemical workstation (Lanlike, Tianjin Lanllike Chemistry Electronic High-tech Co., Ltd.) image data, white light source is AM 1.5G solar simulator (SS50AAA type, U.S. PET company), the useful area of battery is 0.16 cm 2
Gather the electric current I of 400 ~ 800 nm monochromatic ray irradiance and battery, obtain monochromatic ray transformation efficiency IPCE (incident photo-to-current conversion efficient), see attached Fig. 5 and accompanying drawing 6
At simulated solar irradiation AM1.5 (100 mWcm -2) irradiation under, the photoelectric properties parameter is listed in Table 3
Table 3The coumarine dye sensitizing agent IIIThe dye sensitization solar battery performance perameter
Figure 968986DEST_PATH_IMAGE010

Claims (4)

1. the coumarin kind compound shown in a formula (I),
Figure 2013100171053100001DEST_PATH_IMAGE002
I
In formula (I), R is C1-C4 alkylamino radical, C1-C4 alkoxyl group.
2. coumarin kind compound as claimed in claim 1, is characterized in that in described formula (I), R is N (CH 3) 2, OCH 3
3. the method for preparing claim 1 or 2 described coumarin kind compound, it comprises the steps: formula (II) compound and formula III compound are mixed with organic solvent, under the effect of alkaline matter, the reflux stirring reaction, TLC follows the tracks of reaction, after reacting completely, separate out solid, filter, filter cake carries out silica gel column chromatography or carries out recrystallization with recrystallization solvent, the coumarin kind compound shown in acquisition formula (I);
Described recrystallization solvent is one or more in chloroform, methylene dichloride, tetracol phenixin, ethanol or acetone;
One or more in described organic solvent acetonitrile, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane or acetone;
Described alkaline matter is one or more in piperidines, pyridine, triethylamine or dimethylamine;
The ratio of the amount of substance of formula (II) compound and formula (III) compound and alkaline matter is 1:1.0 ~ 3.0:0.1 ~ 1.0, and the organic solvent volumetric usage is counted 2-20mL/mmol. with the amount of substance of formula (II) compound
Figure 2013100171053100001DEST_PATH_IMAGE004
。
4. the application of coumarin kind compound as claimed in claim 1 on solar cell.
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CN103709129A (en) * 2013-12-11 2014-04-09 浙江工业大学 Synthesis and application of diethylamino coumarin dye sensitizer
CN104251849A (en) * 2013-06-25 2014-12-31 温州安得森生物科技有限公司 Application of 4 H-[1]-benzo pyran [4, 3-b] thiophene-2-formic acid hydrazide and derivative thereof in glycoprotein specific fluorescence detection
CN104311543A (en) * 2014-09-25 2015-01-28 浙江工业大学 Synthesis and application of coumarin-containing triarylamine dye sensitizing agent
CN104610251A (en) * 2015-01-29 2015-05-13 浙江工业大学 Coumarin compound as well as preparation method and application thereof
CN110256390A (en) * 2019-06-21 2019-09-20 中国人民解放军第四军医大学 The application of coumarin kind compound, preparation method and preparation treatment cerebral apoplexy drug
CN112939984A (en) * 2021-02-02 2021-06-11 浙江工业大学 Maleimidocarbazole compounds, and preparation method and application thereof
CN116217560A (en) * 2022-12-30 2023-06-06 浙江工业大学 N, N-diethylaminocoumarin compound and preparation method and application thereof

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Cited By (9)

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CN104251849A (en) * 2013-06-25 2014-12-31 温州安得森生物科技有限公司 Application of 4 H-[1]-benzo pyran [4, 3-b] thiophene-2-formic acid hydrazide and derivative thereof in glycoprotein specific fluorescence detection
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CN103709129A (en) * 2013-12-11 2014-04-09 浙江工业大学 Synthesis and application of diethylamino coumarin dye sensitizer
CN104311543A (en) * 2014-09-25 2015-01-28 浙江工业大学 Synthesis and application of coumarin-containing triarylamine dye sensitizing agent
CN104610251A (en) * 2015-01-29 2015-05-13 浙江工业大学 Coumarin compound as well as preparation method and application thereof
CN110256390A (en) * 2019-06-21 2019-09-20 中国人民解放军第四军医大学 The application of coumarin kind compound, preparation method and preparation treatment cerebral apoplexy drug
CN110256390B (en) * 2019-06-21 2020-11-24 中国人民解放军第四军医大学 Coumarin compound, preparation method and application of coumarin compound in preparation of medicine for treating cerebral apoplexy
CN112939984A (en) * 2021-02-02 2021-06-11 浙江工业大学 Maleimidocarbazole compounds, and preparation method and application thereof
CN116217560A (en) * 2022-12-30 2023-06-06 浙江工业大学 N, N-diethylaminocoumarin compound and preparation method and application thereof

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