CN104610251B - A kind of coumarin kind compound and its preparation method and application - Google Patents
A kind of coumarin kind compound and its preparation method and application Download PDFInfo
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- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 150000001875 compounds Chemical class 0.000 title claims abstract description 77
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 41
- 229960000956 coumarin Drugs 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000001235 sensitizing effect Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000010992 reflux Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 150000003053 piperidines Chemical class 0.000 claims description 4
- 239000012065 filter cake Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims 2
- 150000002825 nitriles Chemical class 0.000 claims 1
- 230000009466 transformation Effects 0.000 abstract description 9
- 238000001953 recrystallisation Methods 0.000 abstract description 4
- 238000005481 NMR spectroscopy Methods 0.000 abstract description 2
- 238000012216 screening Methods 0.000 abstract description 2
- 239000000975 dye Substances 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000049 pigment Substances 0.000 description 5
- KIWUVOGUEXMXSV-UHFFFAOYSA-N rhodanine Chemical compound O=C1CSC(=S)N1 KIWUVOGUEXMXSV-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- PQMOXTJVIYEOQL-UHFFFAOYSA-N Cumarin Natural products CC(C)=CCC1=C(O)C(C(=O)C(C)CC)=C(O)C2=C1OC(=O)C=C2CCC PQMOXTJVIYEOQL-UHFFFAOYSA-N 0.000 description 4
- FSOGIJPGPZWNGO-UHFFFAOYSA-N Meomammein Natural products CCC(C)C(=O)C1=C(O)C(CC=C(C)C)=C(O)C2=C1OC(=O)C=C2CCC FSOGIJPGPZWNGO-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000004775 coumarins Chemical class 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000005693 optoelectronics Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000005325 percolation Methods 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- -1 2- thiophene thioamides Chemical class 0.000 description 1
- HIOHRZIAENJDHP-UHFFFAOYSA-N CC(O)=O.N#CC#N Chemical compound CC(O)=O.N#CC#N HIOHRZIAENJDHP-UHFFFAOYSA-N 0.000 description 1
- 241000522215 Dipteryx odorata Species 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical class C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- WORJEOGGNQDSOE-UHFFFAOYSA-N chloroform;methanol Chemical compound OC.ClC(Cl)Cl WORJEOGGNQDSOE-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OBISXEJSEGNNKL-UHFFFAOYSA-N dinitrogen-n-sulfide Chemical compound [N-]=[N+]=S OBISXEJSEGNNKL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 238000001595 flow curve Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 150000002476 indolines Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000002943 quinolinyl group Chemical class N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Plural Heterocyclic Compounds (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
The present invention relates to a kind of coumarin kind compound and its preparation method and application.It is with such as formula（Ⅲ）Shown compound III with such as formula（Ⅳ）Shown compounds Ⅳ or formula（V）Shown compound V is raw material, in the presence of alkali compounds, is heated to reflux stirring reaction certain time, after reaction completely, through filtering, recrystallization acquisition formula（I）Or formula（Ⅱ）Shown coumarin kind compound, its reaction condition is gentle, low for equipment requirements, simple to operate, obtained product structure is through certifications such as nuclear magnetic resonance, the DSSC that the compound is assembled into as dye sensitizing agent has preferable photoelectric transformation efficiency, be dye sensitizing agent screening add it is new can applied material.
Description
Technical field
The present invention relates to a kind of coumarin kind compound and its preparation method and application.
Background technology
DSSC（Dye Sensitized Solar Cell, DSSC）By its cost it is low, can dim light
The features such as Generate, Generation, Generator electricity conversion ratio is not affected by temperature, pole is hopeful substituted for silicon semiconductor optoelectronic converting member, as the next generation
Practical high performance solar cells.Dye sensitizing agent is the crucial knot of decision visible absorption and photoelectric transformation efficiency in DSSC
Structure material, modification and processing is easily designed with structure, the features such as cost is low, stability is good.
The research of Chinese and foreign dyes sensitizer is mainly divided to two classes, and a class is organometallic complex, and Equations of The Second Kind is nonmetallic
Organic dyestuff, with molar absorption coefficient is high, absorption spectrum is wide and can produce excellent chemical property by structural modification modulation
The advantages of, it is the study hotspot of dye sensitizing agent in recent years.Nonmetallic organic dye sensitized dose traditional of general structure is " to give
Body-pi-conjugated bridge-acceptor " (Donor- π Bridge-Acceptor, D- π-A).If on the basis of original D- π-A structures
Increase an acceptor or donor, can not only expand pi-conjugated system, promotion has Smart pigment molecular absorption spectrum Einstein shift, together
When expansion compared to pi-conjugated bridge for be more beneficial for the stability of Smart pigment molecular.For example, Zhu Weihong is equal to indoles
The electrophilic heterocycles such as benzazoles are introduced in quinoline class sensitization pigment molecular, design has synthesized a series of D-A- π-A type indolines
Amboceptor is sensitized pigment, obtains the WS-2 with higher short circuit current flow and open-circuit voltage, and its efficiency is up to 9.04%；Kim etc.
Then introduce diazosulfide and be used as additional receptors, it was recently reported that amboceptor type Coumarins is sensitized pigment HKK-CM4, and gross efficiency is
5.97%。
Cumarin and its derivative are as the electron transporting compound being conjugated in molecule, with excellent fluorescent quantum
Efficiency, high molar absorption coefficient and big Stoke displacements, are widely used in coloring plastic, color fluorescence coating, too
It is positive can collector color fluorescence resin, and the high-technology field such as photosensitive material, light-sensitive material, video disc recording material.By
In being irradiated in visible region responsiveness height, sunshine, stability inferior is good, and Coumarins dye molecule is good as a class development prospect
Good dye sensitizing agent receives extensive concern.The design such as Hara has synthesized a series of Coumarins dye-sensitized molecules, light
Photoelectric transformation efficiency is up to 8.2%；Nearest Kim etc. reports the new D-A- π-A class amboceptor tonka-beans by donor of cumarin
Plain dye-sensitized molecules, gross efficiency is 5.97%；Then designed in great waves and synthesized that new 2D- π-A classes are double to give coumarin dye
Expect sensitizer molecules, its photoelectric transformation efficiency has reached 5.53%.The present invention is using cumarin as donor, and thiazole ring is median receptor,
Thiophene is bridged bond, and cyanoacetic acid or rhodanine acetic acid are that anchor closes acceptor, and it is quick that design has synthesized two new cumarin amboceptor dyestuffs
Agent.At present, there is no literature reported on the solar cell application of the structure.
The content of the invention
In view of the above-mentioned problems existing in the prior art, it is an object of the invention to provide a kind of coumarin kind compound and its
Preparation method and application, the present invention is mainly applied to DSSC.
Described a kind of coumarin kind compound, it is characterised in that including such as formula（Ⅰ）, formula（Ⅱ）Shown chemical compounds I and
Compound ii：
The preparation method of described coumarin kind compound, it is characterised in that comprise the following steps：
1）Involved intermediate and reaction raw materials are respectively such as formula（Ⅲ）Shown compound III, formula（Ⅳ）Shown cyanogen
Acetic acid and formula（Ⅴ）Shown rhodanine acetic acid：
；
2）In organic solvent I, add such as formula（Ⅲ）Shown compound III with such as formula（Ⅳ）Shown cyanoacetic acid or formula
（Ⅴ）Shown rhodanine acetic acid, in the presence of alkali compounds, is heated to reflux stirring reaction, after reaction completely, filters, filter
Cake is recrystallized with organic solvent II, is obtained such as formula（I）Shown compound I or formula（Ⅱ）Shown compound ii.
The preparation method of described coumarin kind compound, it is characterised in that the organic solvent I is acetonitrile.
The preparation method of described coumarin kind compound, it is characterised in that the alkali compounds is piperidines.
The preparation method of described coumarin kind compound, it is characterised in that the organic solvent II is chloroform.
The preparation method of described coumarin kind compound, it is characterised in that formula（Ⅲ）Shown compound III, formula（Ⅳ）
Shown compounds Ⅳ or formula（V）The ratio between shown compound V, amount of material of alkali compounds are 1：1-5-2.5：0.05-
0.15, preferably 1：2.0：0.1.
The preparation method of described coumarin kind compound, it is characterised in that the volumetric usage of organic solvent I is with formula（Ⅲ）
The amount of the material of shown compound III is calculated as 3-6 mL/mmol, preferably 5 mL/mmol.
The preparation method of described coumarin kind compound, it is characterised in that the described reaction time is 4-8h, preferably 6
h。
Application of the described coumarin kind compound as dye sensitizing agent on the solar cell.
Formula（Ⅲ）Shown compound III can be prepared in accordance with the following methods：Will be such as formula（Ⅵ）Shown compound VI,
It is dissolved in DMF, adds Vilsmier reagents, heating response is prepared at 60 DEG C.
Formula（Ⅵ）Shown compound can be prepared in accordance with the following methods：By 3- (2- Bromoacetyls) -7- diethylaminos
Butylcoumariii（Ⅶ）With thiophene 2- thioformamides（Ⅷ）It is dissolved in ethanol, is heated to reflux preparing.
The above-mentioned preparation method being well known to those skilled in the art.
Described coumarin kind compound is as the application of dye sensitizing agent, and concrete application is as follows：
Coumarin kind compound is dissolved in CH3OH-CHCl3（V:V=1:10）In the mixed solvent, soaks TiO2Nano-particle
The h of film optoelectronic pole 24, has been loaded the TiO of coumarin kind compound2Electrode, then the TiO that coumarin kind compound will have been loaded2
Electrode instills electrolyte to electrode assembling with platinum into sandwich structure, and at edge, and battery is introduced using capillary percolation principle
Inside, in 100 mW/cm2Under light intensity irradiation, photovoltage-current characteristic curve is determined.Its result shows such Coumarins
The photoelectric transformation efficiency of compound is 0.33-4.78%.
The reaction equation of the coumarin kind compound of the present invention is as follows：
The present invention is by organic solvent I, with such as formula（Ⅲ）Shown compound III with such as formula（Ⅳ）Shown chemical combination
Thing IV or formula（V）Shown compound V is raw material, in the presence of alkali compounds, is heated to reflux stirring reaction 4-8 h, excellent
6h is selected, after reaction completely, through filtering, recrystallization acquisition formula（I）Or formula（Ⅱ）Shown coumarin kind compound, its reaction condition
Gently, low for equipment requirements, simple to operate, obtained product structure is through certifications such as nuclear magnetic resonance, and the compound is quick as dyestuff
The DSSC that agent is assembled into has preferable photoelectric transformation efficiency, and its photoelectric transformation efficiency is 0.33-
4.78%, be dye sensitizing agent screening add it is new can applied material.
Embodiment
The invention will be further described with reference to embodiments, but protection scope of the present invention is not limited to that：
Embodiment 1：The synthesis of compound VI
3- (2- Bromoacetyls) -7- lignocaines cumarins VII (3.6g, 10.7mmol) are dissolved in absolute ethyl alcohol
In (100mL), 2- thiophene thioamides VIII (1.5g, 10.7mmol) is added, 2 h are heated to reflux.Cooling, suction filtration is obtained
Filter cake recrystallized with absolute ethyl alcohol, be dried to obtain the 2.5g of yellow solid compound VI, yield 61.2%.Fusing point 169 ~ 172
℃；1H NMR (500 MHz, CDCl3) δ: 8.74 (s, 1H, thiazole-H), 8.38 (s, 1H, coumarin-
4-H), 7.59 (d, J = 2.7 Hz, 1H, thiophene-H), 7.54 (d, J = 8.5 Hz, 1H,
thiophene-H), 7.46 (d, J = 4.1 Hz, 1H, coumarin-5-H), 7.42-7.39 (m, 1H,
thiophene-H), 7.13 (dd, J = 5.0, 3.7 Hz, 1H, coumarin-6-H), 7.05 (d, J = 8.4
Hz, 1H, coumarin-8-H), 3.31 (q, J = 7.0 Hz, 4H, CH 2CH3), 1.14 (t, J = 7.1 Hz,
6H, CH2CH 3)。
Embodiment 2：The synthesis of compound III
Under ice bath and drying condition, by POCl3(5 mL) is added dropwise in DMF (5 mL), is stirred half an hour, is obtained
To Vilsmier reagents, compound VI (2.5 g, 6.6mmol) is dissolved in DMF (30 mL), Vilsmier is added
Reagent, 8h is reacted at 60 DEG C.Cooling, reaction solution is poured into frozen water (300 mL), is adjusted with the 10% NaOH aqueous solution
PH=7 are saved, a large amount of precipitations are separated out.Suction filtration, is washed with water (50 mL × 5), then is washed with a large amount of ethanol, after drying
To the g of yellow solid compound III 1.22, the % of yield 45.1.215 ~ 216 DEG C of fusing point;1H NMR (500 MHz, CDCl3)
δ: 10.19 (s, 1H, CHO), 8.44 (s, 1H, thiazole-H), 7.68 (dd, J = 3.8, 1.0 Hz,
1H, coumarin-4-H), 7.53 (dd, J = 5.0, 1.0 Hz, 1H, thiophene-H), 7.42 (d, J=
9.0 Hz, 1H, thiophene-H), 7.15 (dd, J = 5.0, 3.7 Hz, 1H, coumarin-5-H), 6.66
(dd, J = 8.9, 2.5 Hz, 1H, coumarin-6-H), 6.55 (d, J = 2.4 Hz, 1H, coumarin-8-
H), 3.47 (q, J = 7.1 Hz, 4H, CH 2CH3), 1.25 (t, J = 7.1 Hz, 6H, CH2CH 3)。
Embodiment 3：Compound I synthesis
Compound III (0.205 g, 0.5 mmol) and cyanoacetic acid IV (0.085 g, 1.0 mmol) is molten
In acetonitrile (5 mL), piperidines (0.01 mL) is added, 6 h are heated to reflux.Cooling, suction filtration, with acetonitrile (20 mL × 3)
Washing.Dry, CHCl3Recrystallization, obtains the g of dark red solid compound I 0.15, the % of yield 62.9.Fusing point：241~243
℃; 1H NMR (500 MHz, DMSO) δ: 8.29 (s, 1H, CH=CCN), 8.27 (s, 1H, thiazole-H),
7.98 (dd, J = 3.7, 1.0 Hz, 1H, thiophene-H), 7.96 (dd, J = 5.0, 0.9 Hz, 1H,
thiophene-H), 7.62 (d, J = 9.0 Hz, 1H, coumarin-4-H), 7.29 (dd, J = 5.0, 3.8
Hz, 1H, coumarin-5-H), 6.81 (dd, J = 9.0, 2.4 Hz, 1H, coumarin-6-H), 6.64 (d,J = 2.3 Hz, 1H, coumarin-8-H), 3.50 (q, J = 7.0 Hz, 4H, CH 2CH3), 1.17 (t, J =
7.0 Hz, 6H, CH2CH 3); HR-ESI-MS for C24H19N3O4S2: Found: 476.0749 [M-H]-; Calcd.
477.0817。
Embodiment 4：The synthesis of compound ii
Compound III (0.3 g, 0.73 mmol) and rhodanine acetic acid V (281 mg, 1.46 mmol) is molten
In acetonitrile (7 mL), piperidines (0.01 mL) is added, 6 h are heated to reflux.Cooling, suction filtration, with acetonitrile (20 mL × 3)
Washing.Dry, CHCl3Recrystallization, obtains the g of dark red solid compound ii 0.17, the % of yield 40.0.Fusing point 249 ~ 250
℃; 1H NMR (500 MHz, DMSO) δ: 13.49 (bs, 1H, COOH), 8.28 (s, 1H, thiazole-H),
8.01 (dd, J=3.5, 1.0 Hz, 1H, thiophene-H), 7.97 (s, 1H, CH=C), 7.93 (dd, J =
5.0, 1.1 Hz, 1H, thiophene-H), 7.63 (d, J = 9.0 Hz, 1H, coumarin-4-H), 7.29
(dd, J = 5.0, 3.8 Hz, 1H, coumarin-5-H), 6.80 (dd, J = 9.0, 2.4 Hz, 1H,
coumarin-6-H), 6.65 (d, J = 2.3 Hz, 1H, coumarin-8-H), 4.73 (s, 2H, CH 2COOH),
3.50 (q, J = 7.0 Hz, 4H, CH 2CH3), 1.17 (t, J = 7.0 Hz, 6H, CH2CH 3); HR-ESI-MS
for C26H21N3O5S4: Found: 582.0294 [M-H]-; Calcd. 583.0364。
Embodiment 5：Coumarin kind compound as dye sensitizing agent application
The TiO prepared using silk-screen printing2Film of nanoparticles is used as optoelectronic pole：First one is printed on electro-conductive glass FTO
12 μm of thick 20nm of layer TiO2Particle, calcining 30min in Muffle furnace at 450 DEG C.By burned film before material is contaminated
Immerse 0.04 molL-1 TiCl470 DEG C of pretreatment 30min of the aqueous solution, then use water and alcohol flushing, electricity respectively
Blowing drying.After calcining 30min again at 450 DEG C of Muffle furnace, it is cooled to after 80 DEG C and immerses 3 × 10-4 mol·L-1This
The obtained compound I of invention, the methanol of compound ii and chloroformic solution room temperature 24h are sensitized.Preparation to electrode：Using silk
Net printing process, by H2PtCl6Solution is printed on FTO electro-conductive glass, then 400 DEG C of Muffle furnace sintering 20min.Absorptionization
Compound I, compound ii TiO2Electrode instills electrolyte to electrode assembling with platinum into sandwich structure, and at edge（Contain
0.07 mM/L I-）, inside battery is introduced using capillary percolation principle.In 100 mW/cm2Under light intensity irradiation, photoelectricity is determined
Piezo-electric properties of flow curve.Its result is as shown in table 1：
The H of the present invention2PtCl6The configuration of platinum electrode slurry：Weigh 0.1g chloroplatinic acids（H2PtCl6•6H2O）, add ethanol
Solvent supersonic is dissolved, and 5.5g ethyl celluloses are added after filtering, and ultrasonic dissolution 10min adds 4g terpinols, and ultrasonic mixing is equal
It is even, it is spin-dried for solvent and produces sticky platinum electrode slurry.
The DSSC performance parameters that the assembling of the coumarin kind compound of table 1 is obtained
| Compound | Voc (V) | Jsc (mA·cm-2) | ff | η % |
| I | 0.69 | 9.79 | 0.71 | 4.78 |
| Ⅱ | 0.50 | 0.97 | 0.68 | 0.33 |
From table 1 it follows that acceptor is chemical compounds I and chemical combination for the coumarin kind compound of the present invention of cyanoacetic acid
Thing II, there is short circuit current flow and open-circuit voltage, i.e., with photoelectric transformation efficiency, but with dye sensitizing agent I（Chemical compounds I）Acceptor
The dye sensitizing agent that acceptor is rhodanine acetic acid is superior to for its short circuit current flow of the dye sensitizing agent I of cyanoacetic acid and open-circuit voltage
Ⅱ（Compound ii）, thus with higher photoelectric transformation efficiency.
Claims (12)
1. a kind of coumarin kind compound, it is characterised in that structural formula such as formula（Ⅰ）Shown chemical compounds I：
。
2. a kind of preparation method of coumarin kind compound according to claim 1, it is characterised in that comprise the following steps：
1）Involved intermediate and reaction raw materials are respectively such as formula（Ⅲ）Shown compound III, formula（Ⅳ）Shown cyanogen second
Acid：
；
2）In organic solvent I, add such as formula（Ⅲ）Shown compound III with such as formula（Ⅳ）Shown cyanoacetic acid, in alkalization
In the presence of compound, stirring reaction is heated to reflux, after reaction completely, filtering, filter cake is recrystallized with organic solvent II, is obtained
Such as formula（I）Shown compound I.
3. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the organic solvent I is second
Nitrile.
4. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the alkali compounds is
Piperidines.
5. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the organic solvent II is
Chloroform.
6. the preparation method of coumarin kind compound according to claim 2, it is characterised in that formula（Ⅲ）Shown chemical combination
Thing III, formula（Ⅳ）The ratio between shown compounds Ⅳ, amount of material of alkali compounds are 1：1.5-2.5：0.05-0.15.
7. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the volume of organic solvent I is used
Amount is with formula（Ⅲ）The amount of the material of shown compound III is calculated as 3-6 mL/mmol.
8. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the described reaction time is
4-8h。
9. the preparation method of coumarin kind compound according to claim 2, it is characterised in that formula（Ⅲ）Shown chemical combination
Thing III, formula（Ⅳ）The ratio between shown compounds Ⅳ, amount of material of alkali compounds are 1：2.0：0.1.
10. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the volume of organic solvent I
Consumption is with formula（Ⅲ）The amount of the material of shown compound III is calculated as 5 mL/mmol.
11. the preparation method of coumarin kind compound according to claim 2, it is characterised in that the described reaction time is
6 h。
12. a kind of application of coumarin kind compound as claimed in claim 1 as dye sensitizing agent on the solar cell.
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