CN106588789A - Dye sensitizer molecule taking triazole as core and preparation method of dye sensitizer molecule - Google Patents
Dye sensitizer molecule taking triazole as core and preparation method of dye sensitizer molecule Download PDFInfo
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- CN106588789A CN106588789A CN201611115421.4A CN201611115421A CN106588789A CN 106588789 A CN106588789 A CN 106588789A CN 201611115421 A CN201611115421 A CN 201611115421A CN 106588789 A CN106588789 A CN 106588789A
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- 150000003852 triazoles Chemical class 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 60
- 239000002904 solvent Substances 0.000 claims description 53
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 36
- 238000005292 vacuum distillation Methods 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 29
- 239000007787 solid Substances 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000746 purification Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000010898 silica gel chromatography Methods 0.000 claims description 19
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- 238000003786 synthesis reaction Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 13
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 claims description 12
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 claims description 12
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 claims description 12
- UEXCJVNBTNXOEH-UHFFFAOYSA-N phenyl acethylene Natural products C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- MLIREBYILWEBDM-UHFFFAOYSA-N cyanoacetic acid Chemical compound OC(=O)CC#N MLIREBYILWEBDM-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 6
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 6
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 claims description 6
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 5
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 239000012044 organic layer Substances 0.000 claims description 5
- 235000010288 sodium nitrite Nutrition 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 150000003053 piperidines Chemical class 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 230000002093 peripheral effect Effects 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 239000007789 gas Substances 0.000 claims 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims 1
- 229910052740 iodine Inorganic materials 0.000 claims 1
- 239000011630 iodine Substances 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 3
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 239000003208 petroleum Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000000741 silica gel Substances 0.000 description 12
- 229910002027 silica gel Inorganic materials 0.000 description 12
- 229960001866 silicon dioxide Drugs 0.000 description 12
- 239000012046 mixed solvent Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 229910052763 palladium Inorganic materials 0.000 description 8
- -1 Coumarinses Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 150000001345 alkine derivatives Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- NUZWLKWWNNJHPT-UHFFFAOYSA-N anthralin Chemical compound C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O NUZWLKWWNNJHPT-UHFFFAOYSA-N 0.000 description 3
- 229960002311 dithranol Drugs 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 3
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000001235 sensitizing effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011097 chromatography purification Methods 0.000 description 2
- ASWXNYNXAOQCCD-UHFFFAOYSA-N dichloro(triphenyl)-$l^{5}-phosphane Chemical class C=1C=CC=CC=1P(Cl)(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 ASWXNYNXAOQCCD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000434 metal complex dye Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000001117 sulphuric acid Substances 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001716 carbazoles Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
- C07D249/06—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles with aryl radicals directly attached to ring atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
- C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
- C09B23/14—Styryl dyes
- C09B23/143—Styryl dyes the ethylene chain carrying a COOH or a functionally modified derivative, e.g.-CN, -COR, -COOR, -CON=, C6H5-CH=C-CN
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a dye sensitizer molecule taking triazole as a core and a preparation method of the dye sensitizer molecule. According to the dye molecule, a triazole ring is introduced to the design of a molecular structure, and the electronic absorption and transmission capability among D-pi-A dye molecules are greatly improved by substituting donors with different carbon chain lengths and receptors with triple bonds at the periphery, so that a novel triazole dye with high efficiency is obtained. The preparation method of the compound comprises: click chemical reaction, detrimethylsilyl reaction, Sonogashira coupling reaction and the like; and the prepared dye molecule can be applied to a dye-sensitive solar cell and can show favorable photoelectric conversion property so as to have wide application prospects on the aspects of energy development and utilization. In addition, the material also has liquid crystal property under a certain condition so as to also have a huge potential on the aspect of application to photoelectric devices.
Description
Technical field
The invention belongs to technical field of new energies, and in particular to a kind of dye-sensitized molecules with triazole as core and its
Preparation method.
Background technology
DSSC is one of important development direction of solaode, and dye sensitizing agent is to affect battery
The important component of photoelectric transformation efficiency, the also always study hotspot of solar cell material.In DSSC
In, dye sensitizing agent has very important effect, they by absorbing sunlight by the electron excitation of ground state to excited state,
Then the conduction band of quasiconductor is reinjected, and hole is then stayed in dye molecule, realizes the separation of electric charge.The performance of dyestuff is direct
The photoelectric transformation efficiency of DSSC, high performance dye sensitizing agent is affected to need to have the characteristics that：
1) the minimum energy for not occupying track (LUMO) of the electronics of dye molecule should be higher than the energy of semiconductor conduction band edge
Amount, and need to have good Orbital Overlap to be beneficial to the injection of electronics；
2) dye molecule needs the surface for being firmly adsorbed in quasiconductor, such dyestuff to excite the electronics of generation effectively to note
Enter in the conduction band of quasiconductor；
3) dye molecule should have the redox potential than the oxidation-reduction pair corrigendum in electrolyte, such dyestuff
Molecule can obtain quickly being lived again from the electronics of the electrolyte of reduction-state；
4) oxidation state and excited state of dyestuff will have higher stability；
5) dyestuff has good chemical stability under long-term illumination, can complete 108Secondary circular response；
6) dye molecule can be dissolved in the solvent coexisted with quasiconductor, so be conducive in TiO2Surface forms non-agglomerated
Unimolecule dye coating；
7) preferably dyestuff should all have stronger absorption in whole sunlight spectral region.
Through 20 years of researches, the light-sensitive coloring agent developed mainly has metal complex dye and pure organic dye two
Big class.Metal complex dye absorbs generation after sunlight, and metal center is to the electron transition (MLCT) matched somebody with somebody and injects electrons into
This kind of dyestuff mainly includes the multi-pyridine ligand of Ru, Os, Pt etc. in the semiconductor conduction band of light anode, and phthalocyanines and porphyrin are matched somebody with somebody
Compound, wherein study it is most deep be ruthenium coordination compound.Pure organic dye sensitizer absorb sunlight after, by the π of interior molecule-
π*Electron transition is injected electrons in semiconductor conduction band.Pure organic dye mainly include many alkenes, Coumarinses, carbazoles,
The dyestuffs such as indoles, fluorenes class, triphen amine.But, existing organic dyestuff its electricity conversion is not very high.
The content of the invention
In order to overcome the above-mentioned deficiencies of the prior art, it is an object of the invention to provide a kind of dyestuff with triazole as core is quick
Agent molecule and preparation method thereof, is reacted by click chemistry, takes off trimethyl silicane reaction, takes off trimethyl silicane reaction,
Sonogashira coupling reactions, introduce double alkyl electron donors and carboxyl electron acceptor centered on triazole on core, significantly carry
Electron absorption, transmittability between high D- π-A type dye molecules, so as to synthesize a kind of new efficient type dyes.
With low cost, method is simple, with more breakthrough.
To achieve these goals, the technical solution used in the present invention is：
A kind of dye-sensitized molecules with triazole as core, by replacing giving for different carbon chain lengths in peripheral one end
Body, the other end increases the receptors such as carboxyl to strengthen its electrophilic and electron donation, and the compound formula (I) is as follows：
Wherein, R1For formula (a), formula (b), formula (c), formula (d), formula (e)：
The integer of n=1-18 in formula (a), formula (b), formula (c), formula (d), formula (e)；
R2For formula (f), formula (g)：
A kind of preparation method of the dye-sensitized molecules with triazole as core, its synthetic route is as follows：
Preparation process in detail is as follows：
1) to the synthesis of iodobenzene nitrine：
Paraiodoaniline is dissolved in aqueous hydrochloric acid solution, is stirred under 0-5 degrees celsius, sodium nitrite is dissolved in frozen water,
And be added dropwise in reaction vessel；Then Hydrazoic acid,sodium salt is dissolved in frozen water, and is added dropwise in reaction vessel, reacted
20-30 minutes；Dichloromethane extraction product, organic layer is used to be dried with anhydrous magnesium sulfate, filter out and rotate after magnesium sulfate drying, obtained
Dark brown solid is obtained to iodobenzene nitrine；
2) to the synthesis of aldehyde radical phenylacetylene：
a：P-bromobenzaldehyde is dissolved in into tetrahydrofuran and triethylamine mixed solution (volume ratio 1:1) in, ultrasonic aerofluxuss 30-45
Minute, it is subsequently adding the trimethylsilyl acetylene (TMSA) of 1-2 equivalents, the triphenyl phosphorus palladium chloride of 2-5 equivalents, 3-5 equivalents
Hydro-Giene (Water Science).；Argon protection 8-10 hour of lower reaction；Vacuum distillation removes silica gel column chromatography purification after solvent, revolving, vacuum
Dry white solid.
b：Product in step (a) is dissolved in methanol and tetrahydrofuran solution, is subsequently adding under Anhydrous potassium carbonate, room temperature and is stirred
4-6 hour is mixed, vacuum distillation removes solvent, and silica gel column chromatography is slightly purified, and white solid is obtained after vacuum drying, in a reservoir
Logical nitrogen protection, is obtained to aldehyde radical phenylacetylene；
(3) synthesis of end-product：
A, equimolar amountss are dissolved in N-N dimethylformamides, at room temperature to iodobenzene nitrine and to aldehyde radical phenylacetylene
Logical argon stirs 10-20 minutes, adds the Hydro-Giene (Water Science). of 3-5 equivalents, argon to protect lower 80-100 degree Celsius of back flow reaction 8-10
Hour；Vacuum distillation removes solvent, and silica gel column chromatography purification, revolving is vacuum dried to obtain light yellow solid intermediate 1；
B, the R1 in product Intermediate in step (a) 1 and formula is dissolved in into tetrahydrofuran and triethylamine mixed solution (volume
Than 1:1) in, ultrasonic aerofluxuss 30-45 minutes, the triphenyl phosphorus palladium chloride of 2-5 equivalents, the Hydro-Giene (Water Science). of 3-5 equivalents；Argon is protected
Shield 8-10 hour of lower reaction；Vacuum distillation removes silica gel column chromatography purification after solvent, rotates, is vacuum dried to obtain faint yellow solid
Intermediate 2；
C, product Intermediate in step (b) 2 is dissolved in appropriate acetonitrile solvent with appropriate cyanoacetic acid, Deca is a small amount of
Catalyst piperidines, 3-8 hours are stirred at reflux under 80-100 degree Celsius, (or product Intermediate 2 is molten with ethanedioic acid in step (b)
In pyridine solvent, appropriate aniline reaction is added) vacuum distillation removes silica gel column chromatography purification after solvent, revolving, vacuum drying
Light yellow solid is obtained, the dye-sensitized molecules with triazole as core are obtained.
The invention has the beneficial effects as follows：
1) present invention is by a kind of new synthetic reaction --- and click chemistry has been applied in the preparation process of material,
It is prepared for the new type dyes of a class.
2) with wide absorption bandses, and its photovoltage and photoelectricity can be controlled by adjusting the length of alkyl chain
Stream.
3) due between the π-π interactions between the fragrant kernel of the dyestuff electron cloud enrichment and peripheral aliphatic chain
Van der Waals force collective effect is possible to make material have liquid crystal liquid crystal property under certain condition, has in the application aspect of photoelectric device
Huge potentiality.
Description of the drawings
Fig. 1 is the synthetic route of dye molecule.
Fig. 2 is the UV collection of illustrative plates of the molecule of embodiment 1.
Specific embodiment
The present invention is further discussed below with reference to embodiments, but the present invention is not limited to following examples.
Embodiment 1
Prepared by this example is the dye molecule described in formula, and wherein R1 isWherein n=12, R2 areReactions steps are as follows：
(1) to the synthesis of iodobenzene nitrine：
14.4mmol (3.15g) paraiodoaniline is dissolved in into (HCl in 9.1ml aqueous hydrochloric acid solutions：Water=1:1), it is placed in
100ml small beakers, stir under 0 degrees celsius, and 14.4mmol (1.00g) sodium nitrite is dissolved in 51.3ml frozen water, and by
In being added dropwise to reaction beaker, 14.4mmol (0.94g) Hydrazoic acid,sodium salt is dissolved in 11.3ml frozen water, is then added dropwise to reaction
In container, react 30 minutes.Use dichloromethane extraction product, organic layer to be dried with 2.00g anhydrous magnesium sulfates, filter out magnesium sulfate
After rotate, product is placed in vacuum drying oven, dry 3.29g dark brown solids, yield is 93.5%.
(2) synthesis of R1：
a：20.0mmol (4.38g) paraiodoanilines and 80.0mmol (19.92g) bromododecane are dissolved in into 60ml N-N bis-
During 250ml single necked round bottom flask is placed in methylformamide, 60mmol (8.28g) potassium carbonate and 60.0mmol (9.96g) are added
Potassium iodide, leads at room temperature argon and stirs 10 minutes, and argon protects lower 100 degrees Celsius of back flow reaction 10 hours.Vacuum distillation is removed
Solvent is removed, (developing solvent is dichloromethane and petroleum ether 1 for silicagel column purification:9 mixed solvent) 9.56g light yellow liquids are obtained, produce
Rate is 86.1%.
b：Product in 15.0mmol (8.3g) a is dissolved in into 90ml tetrahydrofurans and triethylamine mixed solution (volume ratio 1:1)
In, in being placed in 250ml single-necked flasks, ultrasonic aerofluxuss 45 minutes are subsequently adding the trimethylsilyl acetylene of 18.0mmol (1.76g).
Add 96.5mg triphenyl phosphorus palladium chlorides, 48.3mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.After stopped reaction,
Vacuum distillation removes silica gel column chromatography purification after solvent, and (developing solvent is dichloromethane:Petroleum ether is 1:4), revolving, vacuum drying
5.59g weak yellow liquids are obtained, yield is 71%.
c：Product in 8.0mmol (4.2g) b is dissolved in 25ml methanol and 55ml tetrahydrofuran solutions, 250ml is placed in mono-
In mouth round-bottomed flask, Anhydrous potassium carbonate is subsequently adding, 5 hours are stirred under room temperature, vacuum distillation removes solvent, silicagel column (exhibition
Agent is opened for petroleum ether and dichloromethane 1：1 mixed solvent) thick purification；3.04g weak yellow liquids, yield are obtained after vacuum drying
For 84%.
(3) to the synthesis of aldehyde radical phenylacetylene：
a：15.0mmol (2.78g) p-bromobenzaldehyde is dissolved in into 95ml tetrahydrofurans and triethylamine mixed solution (volume ratio
1:1) in, in being placed in 250ml single-necked flasks, ultrasonic aerofluxuss 45 minutes are subsequently adding the trimethyl silicane second of 18.0mmol (1.76g)
Alkynes.Add 97.2mg triphenyl phosphorus palladium chlorides, 46.5mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.Stopped reaction
Afterwards, vacuum distillation remove solvent after silica gel column chromatography purification (developing solvent is dichloromethane:Petroleum ether is 1:4), revolving, vacuum are done
Dry to obtain 2.19g white solids, yield is 72.3%.
b：Product in 8.0mmol (1.62g) a is dissolved in 30ml methanol and 60ml tetrahydrofuran solutions, 250ml is placed in mono-
In mouth round-bottomed flask, Anhydrous potassium carbonate is subsequently adding, 5 hours are stirred under room temperature, vacuum distillation removes solvent, silicagel column (exhibition
Agent is opened for petroleum ether and dichloromethane 1：1 mixed solvent) thick purification；0.88g white solids are obtained after vacuum drying, yield is
85.1%.
(4) synthesis of end-product：
a：6.0mmol (1.31g) is dissolved in into 35ml N-N to iodobenzene nitrine and 6.0mmol (0.77g) to aldehyde radical phenylacetylene
During 100ml single necked round bottom flask is placed in dimethylformamide, argon is led at room temperature and is stirred 10 minutes, add 54.5mg iodate
Cuprous, argon protects lower 100 degrees Celsius of back flow reaction 10 hours.Vacuum distillation removes solvent, and (developing solvent is second for silicagel column purification
Acetoacetic ester and petroleum ether 1:4 mixed solvent) 1.78g light yellow solids are obtained, yield is 79.3%.
b：Product in 4.0mmol (1.49g) a and 4.8mmol (2.17g) R1 are mixed in 40ml tetrahydrofurans and triethylamine
Solution (volume ratio 1:1) in, in being placed in 100ml single-necked flasks, ultrasonic aerofluxuss 45 minutes add 24.2mg triphenyl phosphorus dichlorides
Palladium, 12.3mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.After stopped reaction, vacuum distillation removes silicagel column after solvent
Chromatographic purification (developing solvent is dichloromethane), rotates, is vacuum dried to obtain 1.82g weak yellow liquids, and yield is 65%.
c：Product in 2.0mmol (1.4g) b and 2.6mmol (0.22g) cyanoacetic acid are dissolved in 15ml acetonitriles, Deca
One drop piperidines, in 90 degrees Celsius of lower back flow reaction 8 hours.After stopped reaction, vacuum distillation removes silica gel column chromatography after solvent and carries
Pure (developing solvent is ethyl acetate), rotates, is vacuum dried to obtain 0.95g faint yellow solids, and yield is 62%.
The data that the monomer is measured are as follows：
1H-NMR(300MHz,CDCl3):δ=11.01 (s, 1H), 8.29 (s, 1H), 8.11 (s, 1H), 8.08 (d, J=
6.0Hz, 2H), 7.97 (d, J=6.0Hz, 2H), 7.74 (d, J=6.0Hz, 2H), 7.64 (d, J=6.0Hz, 2H), 7.36 (d,
J=6.0Hz, 2H), 6.56 (d, J=6.0Hz, 2H), 3.26 (t, 4H), 1.53 (m, 4H), 1.27 (m, 36H), 0.86 (t, 6H)
ppm；FT-IR(KBr):ν=3112,2923,2852,2239,2211,2190,1693,1604,1568,1522,1484,
1466,1415,1402,1368,1293,1207,1183,1144,1060,816,720MALDI-TOF-MS(dithranol):
m/z:calcd for C50H65N5O2:768.08g mol-1,found:768.27g mol-1[MH]+；elemental
Analysis calcd (%) for C50H65N5O2(768.08):C 78.19,H 8.53,N 9.12,O 4.17；found:C
78.27,H 8.42,N 9.02,O 4.26.
Embodiment 2
Prepared by this example is the dye molecule described in formula, and R1 isWherein n=4, R2 areReactions steps are as follows：
(1) to the synthesis of iodobenzene nitrine：
10.0mmol (2.19g) paraiodoaniline is dissolved in into (HCl in 6.5ml aqueous hydrochloric acid solutions：Water=1:1), it is placed in
100ml small beakers, stir under 0 degrees celsius, and 10.0mmol (0.69g) sodium nitrite is dissolved in 35.4ml frozen water, and
In being added dropwise to reaction beaker, 10.0mmol (0.65g) Hydrazoic acid,sodium salt is dissolved in 7.8ml frozen water, is then added dropwise to anti-
In answering container, react 30 minutes.Use dichloromethane extraction product, organic layer to be dried with 2.00g anhydrous magnesium sulfates, filter out sulphuric acid
Rotate after magnesium, product is placed in vacuum drying oven, dry 2.25g dark brown solids, yield is 92%.
(2) to the synthesis of aldehyde radical phenylacetylene：
a：12.0mmol (2.22g) p-bromobenzaldehyde is dissolved in into 75ml tetrahydrofurans and triethylamine mixed solution (volume ratio
1:1) in, in being placed in 250ml single-necked flasks, ultrasonic aerofluxuss 45 minutes are subsequently adding the trimethyl silicane second of 16.0mmol (1.56g)
Alkynes.Add 72.3mg triphenyl phosphorus palladium chlorides, 36.5mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.Stopped reaction
Afterwards, vacuum distillation remove solvent after silica gel column chromatography purification (developing solvent is dichloromethane:Petroleum ether is 1:4), revolving, vacuum are done
Dry to obtain 1.75g white solids, yield is 73.1%.
b：Product in 8.0mmol (1.62g) a is dissolved in 30ml methanol and 60ml tetrahydrofuran solutions, 250ml is placed in mono-
In mouth round-bottomed flask, Anhydrous potassium carbonate is subsequently adding, 4.5 hours are stirred under room temperature, vacuum distillation removes solvent, silicagel column
(developing solvent is petroleum ether and dichloromethane 1：1 mixed solvent) thick purification；0.87g white solids are obtained after vacuum drying, is produced
Rate is 84.8%.
(3) synthesis of end-product：
a：6.0mmol (1.31g) is dissolved in into 35ml N-N to iodobenzene nitrine and 6.0mmol (0.77g) to aldehyde radical phenylacetylene
During 100ml single necked round bottom flask is placed in dimethylformamide, argon is led at room temperature and is stirred 10 minutes, add 53.8mg iodate
Cuprous, argon protects lower 100 degrees Celsius of back flow reaction 10 hours.Vacuum distillation removes solvent, and (developing solvent is second for silicagel column purification
Acetoacetic ester and petroleum ether 1:4 mixed solvent) 1.79g light yellow solids are obtained, yield is 80%.
b：By product in 4.0mmol (1.49g) a and 4.8mmol (0.78g) 1- acetenyls -3- butyl-thiophene in 40ml tetra-
Hydrogen furan and triethylamine mixed solution (volume ratio 1:1) in, in being placed in 100ml single-necked flasks, ultrasonic aerofluxuss 45 minutes are added
24.2mg triphenyl phosphorus palladium chlorides, 13.5mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.After stopped reaction, decompression
Silica gel column chromatography purification (developing solvent is dichloromethane) after solvent is distilled off, is rotated, is vacuum dried to obtain 1.1g faint yellow solids,
Yield is 65.5%.
c：Product in 2.0mmol (0.85g) b and 2.6mmol (0.22g) cyanoacetic acid are dissolved in 15ml acetonitriles, are dripped
Drop piperidines of plus one, in 90 degrees Celsius of lower back flow reaction 9 hours.After stopped reaction, vacuum distillation removes silica gel column chromatography after solvent
Purification (developing solvent is ethyl acetate), rotates, is vacuum dried to obtain 0.59g faint yellow solids, and yield is 59.8%.
The data that the monomer is measured are as follows：
1H-NMR(300MHz,CDCl3):δ=11.02 (s, 1H), 8.27 (s, 1H), 8.11 (s, 1H), 8.06 (d, J=
6.0Hz, 2H), 7.95 (d, J=6.0Hz, 2H), 7.74 (d, J=6.0Hz, 2H), 7.64 (d, J=6.0Hz, 2H), 6.89 (s,
1H),6.63(s,1H),2.55(t,2H),1.62(m,2H),1.33(m,2H),0.96(t,3H)ppm；FT-IR(KBr):ν=
3115,3099,3077,2924,2852,2238,2209,2190,1692,1604,1568,1522,1484,1467,1412,
1401,1368,1293,1207,1183,1145,1060,817,722MALDI-TOF-MS(dithranol):m/z:calcd
for C29H24N4O2S:492.16g mol-1,found:492.59g mol-1[MH]+；elemental analysis calcd
(%) for C29H24N4O2S(492.59):C 70.71,H 4.91,N 11.37,O 6.50,S 6.51.found:C 70.61,
H 4.98,N 11.46,O 6.61,S 6.54.
Embodiment 3
Prepared by this example is the dye molecule described in formula, and R1 isWherein n=4, R2 areIt is as follows for reactions steps：
(1) to the synthesis of iodobenzene nitrine：
11.0mmol (2.41g) paraiodoaniline is dissolved in into (HCl in 7.2ml aqueous hydrochloric acid solutions：Water=1:1), it is placed in
100ml small beakers, stir under 0 degrees celsius, and 11.0mmol (0.76g) sodium nitrite is dissolved in 35.4ml frozen water, and
In being added dropwise to reaction beaker, 11.0mmol (0.72g) Hydrazoic acid,sodium salt is dissolved in 8.6ml frozen water, is then added dropwise to anti-
In answering container, react 30 minutes.Use dichloromethane extraction product, organic layer to be dried with 2.00g anhydrous magnesium sulfates, filter out sulphuric acid
Rotate after magnesium, product is placed in vacuum drying oven, dry 2.39g dark brown solids, yield is 89%.
(2) synthesis of R1：
a：20.0mmol (4.38g) paraiodoanilines and 80.0mmol (10.88g) bromination of n-butane are dissolved in into 65ml N-N bis-
During 250ml single necked round bottom flask is placed in methylformamide, 60mmol (8.28g) potassium carbonate and 60.0mmol (9.96g) are added
Potassium iodide, leads at room temperature argon and stirs 15 minutes, and argon protects lower 100 degrees Celsius of back flow reaction 10 hours.Vacuum distillation is removed
Solvent is removed, (developing solvent is dichloromethane and petroleum ether 1 for silicagel column purification:9 mixed solvent) 5.68g light yellow liquids are obtained, produce
Rate is 85.9%.
b：Product in 15.0mmol (4.97g) a is dissolved in into 90ml tetrahydrofurans and triethylamine mixed solution (volume ratio 1:1)
In, in being placed in 250ml single-necked flasks, ultrasonic aerofluxuss 50 minutes are subsequently adding the trimethylsilyl acetylene of 18.0mmol (1.76g).
Add 94.2mg triphenyl phosphorus palladium chlorides, 45.7mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.After stopped reaction,
Vacuum distillation removes silica gel column chromatography purification after solvent, and (developing solvent is dichloromethane:Petroleum ether is 1:4), revolving, vacuum drying
3.29g weak yellow liquids are obtained, yield is 72.9%.
c：Product in 9.0mmol (2.71g) b is dissolved in 30ml methanol and 60ml tetrahydrofuran solutions, 250ml is placed in mono-
In mouth round-bottomed flask, Anhydrous potassium carbonate is subsequently adding, 5 hours are stirred under room temperature, vacuum distillation removes solvent, silicagel column (exhibition
Agent is opened for petroleum ether and dichloromethane 1：1 mixed solvent) thick purification；1.73g weak yellow liquids, yield are obtained after vacuum drying
For 84.5%.
(3) to the synthesis of aldehyde radical phenylacetylene：
a：15.0mmol (2.78g) p-bromobenzaldehyde is dissolved in into 100ml tetrahydrofurans and triethylamine mixed solution (volume ratio
1:1) in, in being placed in 250ml single-necked flasks, ultrasonic aerofluxuss 50 minutes are subsequently adding the trimethyl silicane second of 18.0mmol (1.76g)
Alkynes.Add 95.3mg triphenyl phosphorus palladium chlorides, 44.7mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.Stopped reaction
Afterwards, vacuum distillation remove solvent after silica gel column chromatography purification (developing solvent is dichloromethane:Petroleum ether is 1:4), revolving, vacuum are done
Dry to obtain 2.24g white solids, yield is 74.1%.
b：Product in 8.0mmol (1.62g) a is dissolved in 30ml methanol and 60ml tetrahydrofuran solutions, 250ml is placed in mono-
In mouth round-bottomed flask, Anhydrous potassium carbonate is subsequently adding, 5 hours are stirred under room temperature, vacuum distillation removes solvent, silicagel column (exhibition
Agent is opened for petroleum ether and dichloromethane 1：1 mixed solvent) thick purification；0.87g white solids are obtained after vacuum drying, yield is
84.2%.
(4) synthesis of end-product：
a：6.0mmol (1.31g) is dissolved in into 33ml N-N to iodobenzene nitrine and 6.0mmol (0.77g) to aldehyde radical phenylacetylene
During 100ml single necked round bottom flask is placed in dimethylformamide, argon is led at room temperature and is stirred 15 minutes, add 53.2mg iodate
Cuprous, argon protects lower 100 degrees Celsius of back flow reaction 10 hours.Vacuum distillation removes solvent, and (developing solvent is second for silicagel column purification
Acetoacetic ester and petroleum ether 1:4 mixed solvent) 1.82g light yellow solids are obtained, yield is 81.4%.
b：Product in 4.0mmol (1.49g) a and 4.8mmol (1.09g) R1 are mixed in 45ml tetrahydrofurans and triethylamine
Solution (volume ratio 1:1) in, in being placed in 100ml single-necked flasks, ultrasonic aerofluxuss 45 minutes add 25.3mg triphenyl phosphorus dichlorides
Palladium, 13.1mg Hydro-Giene (Water Science) .s.Argon protection 10 hours of lower reaction.After stopped reaction, vacuum distillation removes silicagel column after solvent
Chromatographic purification (developing solvent is dichloromethane), rotates, is vacuum dried to obtain 1.21g faint yellow solids, and yield is 63.5%.
c：Product in 2.0mmol (0.95g) b and 2.2mmol (0.198g) ethanedioic acid are dissolved in 20ml pyridines, are added
0.4mmol (0.037g) aniline, in 115 degrees Celsius of lower back flow reaction 10 hours.After stopped reaction, vacuum distillation is removed after solvent
Silica gel column chromatography purifies (developing solvent is ethyl acetate), rotates, is vacuum dried to obtain 0.63g faint yellow solids, and yield is 61.1%.
The data that the monomer is measured are as follows：
1H-NMR(300MHz,CDCl3):δ=11.01 (s, 1H), 8.28 (s, 1H), 8.10 (s, 1H), 8.06 (d, J=
6.0Hz, 2H), 7.95 (d, J=6.0Hz, 2H), 7.73 (d, J=6.0Hz, 2H), 7.63 (d, J=6.0Hz, 2H), 7.35 (d,
J=6.0Hz, 2H), 6.55 (d, J=6.0Hz, 2H), 6.41 (s, 1H), 3.26 (t, 4H), 1.53 (m, 4H), 1.28 (m, 4H),
0.88(t,6H)ppm；FT-IR(KBr):ν=3102,2925,2857,2212,2191,1693,1605,1567,1522,
1483,1466,1417,1402,1368,1293,1207,1183,1144,1060,817,722MALDI-TOF-MS
(dithranol):m/z:calcd for C33H34N4O2:518.27g mol-1,found:518.65g mol-1[MH]+；
Elemental analysis calcd (%) for C33H34N4O2(518.65):C 76.42,H 6.61,N 10.80,O
6.17；found:C 76.38,H 6.58,N 10.84,O 6.23.
Embodiment 4
When it is 1～18 different length linear paraffin to be n in formula, according to embodiment 1 different direct-connected alkane are respectively synthesized
D- π-A type dyes the molecules of hydrocarbon, and the photoelectric current under its different alkyl chain, photovoltage, transformation efficiency are tested,
Resulting result is as shown in table 1.
Table 1
Table 1：The photoelectric properties test of the D- π-A type triazole dye molecules of different length linear paraffin.
Claims (2)
1. a kind of dye-sensitized molecules with triazole as core, it is characterised in that by replacing different carbon chain in peripheral one end
The donor of length, the other end increases the receptors such as carboxyl to strengthen its electrophilic and electron donation, and the compound formula (I) is such as
Under：
Wherein, R1For formula (a), formula (b), formula (c), formula (d), formula (e)：
The integer of n=1-18 in formula (a), formula (b), formula (c), formula (d), formula (e)；
R2For formula (f), formula (g)：
2. a kind of preparation method of the dye-sensitized molecules with triazole as core, it is characterised in that its synthetic route is as follows：
Preparation process in detail is as follows：
1) to the synthesis of iodobenzene nitrine：
Paraiodoaniline is dissolved in aqueous hydrochloric acid solution, is stirred under 0-5 degrees celsius, sodium nitrite is dissolved in frozen water, and by
In being added dropwise to reaction vessel；Then Hydrazoic acid,sodium salt is dissolved in frozen water, and is added dropwise in reaction vessel, react 20-30
Minute；Use dichloromethane extraction product, organic layer to be dried with anhydrous magnesium sulfate, filter out and rotate after magnesium sulfate drying, obtain dark brown
Color solid is obtained to iodobenzene nitrine；
2) to the synthesis of aldehyde radical phenylacetylene：
a：P-bromobenzaldehyde is dissolved in into tetrahydrofuran and triethylamine mixed solution (volume ratio 1:1) in, ultrasonic aerofluxuss 30-45 point
Clock, is subsequently adding the trimethylsilyl acetylene (TMSA) of 1-2 equivalents, the triphenyl phosphorus palladium chloride of 2-5 equivalents, the iodine of 3-5 equivalents
Change cuprous；Argon protection 8-10 hour of lower reaction；Vacuum distillation removes silica gel column chromatography purification after solvent, and revolving, vacuum are done
It is dry to obtain white solid；
b：Product in step (a) is dissolved in methanol and tetrahydrofuran solution, is subsequently adding under Anhydrous potassium carbonate, room temperature and is stirred 4-
6 hours, vacuum distillation removes solvent, and silica gel column chromatography is slightly purified, and white solid is obtained after vacuum drying, and nitrogen is led in a reservoir
Gas shielded, is obtained to aldehyde radical phenylacetylene；
(3) synthesis of end-product：
A, equimolar amountss are dissolved in N-N dimethylformamides to iodobenzene nitrine and to aldehyde radical phenylacetylene, argon is led at room temperature
Gas agitating 10-20 minutes, the Hydro-Giene (Water Science). of 3-5 equivalents, argon is added to protect lower 80-100 degree Celsius of back flow reaction 8-10 hour；
Vacuum distillation removes solvent, and silica gel column chromatography purification, revolving is vacuum dried to obtain light yellow solid intermediate 1；
B, the R1 in product Intermediate in step (a) 1 and formula is dissolved in into tetrahydrofuran and triethylamine mixed solution (volume ratio 1:
1) in, ultrasonic aerofluxuss 30-45 minutes, the triphenyl phosphorus palladium chloride of 2-5 equivalents, the Hydro-Giene (Water Science). of 3-5 equivalents；Under argon protection
8-10 hour of reaction；Vacuum distillation removes silica gel column chromatography purification after solvent, rotate, be vacuum dried in the middle of faint yellow solid
Body 2；
C, product Intermediate in step (b) 2 and appropriate cyanoacetic acid are dissolved in appropriate acetonitrile solvent, Deca is a small amount of to urge
Agent piperidines, is stirred at reflux 3-8 hours under 80-100 degree Celsius, (or product Intermediate 2 is dissolved in pyrrole with ethanedioic acid in step (b)
In pyridine solvent, appropriate aniline reaction is added) vacuum distillation removes silica gel column chromatography purification after solvent, and rotate, be vacuum dried shallow
Yellow solid, obtains the dye-sensitized molecules with triazole as core.
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| CN108191917B (en) * | 2018-01-09 | 2020-05-05 | 中国科学技术大学 | Automatic-regulation photoelectric conversion molecule and preparation method thereof |
| CN108192640A (en) * | 2018-01-25 | 2018-06-22 | 西京学院 | Monomer liquid crystal of the huge electrocaloric effect of difluoro methoxy bridge bond low viscosity and preparation method thereof |
| CN108192640B (en) * | 2018-01-25 | 2021-05-28 | 西京学院 | Monomer liquid crystal with difluoromethoxy bridge bond low-viscosity giant electrothermal effect and preparation method thereof |
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