CN104844562B - A kind of many thienyl triphenylamine compounds and preparation method and application - Google Patents
A kind of many thienyl triphenylamine compounds and preparation method and application Download PDFInfo
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- CN104844562B CN104844562B CN201510283731.6A CN201510283731A CN104844562B CN 104844562 B CN104844562 B CN 104844562B CN 201510283731 A CN201510283731 A CN 201510283731A CN 104844562 B CN104844562 B CN 104844562B
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- -1 thienyl triphenylamine compounds Chemical class 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- 150000001412 amines Chemical class 0.000 claims description 35
- 229910052757 nitrogen Inorganic materials 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- TUCRZHGAIRVWTI-UHFFFAOYSA-N 2-bromothiophene Chemical compound BrC1=CC=CS1 TUCRZHGAIRVWTI-UHFFFAOYSA-N 0.000 claims description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 125000001544 thienyl group Chemical group 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 239000002904 solvent Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N formic acid Substances OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000004440 column chromatography Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003480 eluent Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000012141 concentrate Substances 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N Pd(PPh3)4 Substances [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 230000005526 G1 to G0 transition Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 230000008033 biological extinction Effects 0.000 abstract description 5
- 230000001235 sensitizing effect Effects 0.000 abstract description 5
- 239000000975 dye Substances 0.000 description 32
- 238000006243 chemical reaction Methods 0.000 description 9
- 206010070834 Sensitisation Diseases 0.000 description 6
- 230000008313 sensitization Effects 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Substances CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000007789 sealing Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical class C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WUOACPNHFRMFPN-VIFPVBQESA-N (R)-(+)-alpha-terpineol Chemical compound CC1=CC[C@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-VIFPVBQESA-N 0.000 description 1
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical class CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LWISLHRIEATKTM-UHFFFAOYSA-N 2-Ethynylthiophene Chemical compound C#CC1=CC=CS1 LWISLHRIEATKTM-UHFFFAOYSA-N 0.000 description 1
- PJRGDKFLFAYRBV-UHFFFAOYSA-N 2-phenylthiophene Chemical compound C1=CSC(C=2C=CC=CC=2)=C1 PJRGDKFLFAYRBV-UHFFFAOYSA-N 0.000 description 1
- RFFFKMOABOFIDF-UHFFFAOYSA-N Pentanenitrile Chemical compound CCCCC#N RFFFKMOABOFIDF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- XAXHEVRKPSEDKX-UHFFFAOYSA-N cyanic acid;guanidine Chemical compound [O-]C#N.NC([NH3+])=N XAXHEVRKPSEDKX-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000000119 electrospray ionisation mass spectrum Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000006617 triphenylamine group Chemical group 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D333/38—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- 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
- C09B57/00—Other synthetic dyes of known constitution
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Photovoltaic Devices (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a kind of many thienyl triphenylamine compounds and preparation method and application.The structural formula of many thienyl triphenylamine compounds of the present invention is as follows：.The many thienyl triphenylamine compound synthetic routes of the present invention are simple, low cost, molar extinction coefficient are high, can be as dye sensitizing agent, for DSSC.
Description
Technical field
The present invention relates to a kind of many thienyl triphenylamine compounds, and in particular to one kind can be used for dye sensitization of solar
Many thienyl triphen amine dye sensitizing agents of battery.
Background technology
In past 20 years, DSSC (DSSCs) is due to relatively low manufacturing cost and higher energy
Transformation efficiency is measured, the extensive concern of industrial quarters and academia is caused.During photoelectron changes into electric current, dye sensitization
Agent plays vital effect in the aspect of performance for determining solar cell.Compared with rare precious metals ruthenium complex dyestuff,
Sensitizing dyestuff without noble metal more agrees with pursuit of the people to economic and environment-friendly photovoltaic system.Because triphenylamine units have very strong
Electron supplying capacity and hole transport performance, so, it is to carry to carry out design and rational and structure regulating to triphen amine dye sensitizing agent
A kind of most direct, maximally effective approach of high DSSCs battery performances.
Triphen amine dye sensitizing agent generally existing complex synthetic route of the prior art, molar extinction coefficient be relatively low,
The shortcoming that cost is higher, stability is not high, it is impossible to meet the demand of solar cell.
The content of the invention
The invention aims to solve defect present in prior art, there is provided a kind of synthetic route is simple, cost
The high many thienyl triphen amine D- π-A type dyes of low, molar extinction coefficient.
In order to achieve the above object, the invention provides a kind of many thienyl triphenylamine compounds, many thienyls three
The structural formula of amino benzenes compounds is as follows：
Present invention also offers the preparation method of above-mentioned many thienyl triphenylamine compounds, comprise the following steps：In argon
Under gas shielded, 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine and 5-acetenyl thiophene are added in three-necked bottle
Fen-2-formic acid, after being dissolved using tetrahydrofuran and triethylamine as solvent, is deaerated 15-30 minutes with nitrogen displacement；Then, in nitrogen
Under protection Pd (PPh are added to middle solution3)4And CuI, and stirred 24-48 hours at 35-55 DEG C, purifying produces many thiophenes
Fen base triphenylamine compound.
Wherein, 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine and 5-thiophene acetylene-2-formic acid
Mol ratio be 1:2-1:5, preferably 1:3；The consumption of the tetrahydrofuran is every 100 milligrams of 4- (5- bromothiophene bases phenyl)-N,
N- bis- (4- thienyls phenyl) amine adds 5-100 milliliters, and preferable amount is 0.1mmol 4- (5- bromothiophene bases phenyl)-N, N-
Two (4- thienyls phenyl) amine add 30 milliliters；The consumption of the triethylamine is every 100 milligrams of 4- (5- bromothiophene bases phenyl)-N,
N- bis- (4- thienyls phenyl) amine adds 2-20 milliliters, and preferable amount is 0.1mmol 4- (5- bromothiophene bases phenyl)-N, N- bis-
(4- thienyls phenyl) amine adds 5 milliliters；Pd (the PPh3)4With 4- (5- bromothiophene bases phenyl)-N, (the 4- thienyl benzene of N- bis-
Base) amine mol ratio be 0.01:1-0.2:1, preferably 1:10；Pd (the PPh3)4Mol ratio with CuI is 1:1.
Above-mentioned purge process is purified using column chromatography, and eluant, eluent uses dichloromethane and methanol mixed solution, collects elution
After liquid, concentrate drying produces many thienyl triphenylamine compounds；The volume ratio of the dichloromethane and methanol is 10:
0.5-10:1.5, preferably 9:1.The stationary phase of column chromatography uses the silica gel of 200-300 mesh.
After eluent concentrate drying, recrystallized using the mixed solvent of dichloromethane and methanol；The recrystallization is mixed
The volume ratio of dichloromethane and methanol is in bonding solvent：5:1-15:1, preferably 9:1.
Present invention also offers application of the above-mentioned many thienyl triphenylamine compounds in DSSC.
The light anode of DSSC is prepared using following steps：
（1）Prepare dye solution：Many thienyl triphenylamine compounds are dissolved in the mixed solution of methane and ethanol
In；The concentration of many thienyl triphenylamine compounds is 0.4mmol/L；The volume ratio of the methane and ethanol is 3:2；
（2）It is prepared by light anode：By TiO2Electrode is placed in step（1）24-48h is soaked in the dye solution prepared, i.e.,
.
The TiO of dyestuff will be soaked2Electrode clean is dried, and Pt is plated in the way of evaporation on punching electro-conductive glass is made
To electrode, two plate electrodes formation cavity is fixed with heat-sealing film, electrolyte solution is injected in cavity, then seal the electrolysis of Pt electrodes
Liquid orifice, that is, be made DSSC batteries.
The present invention has advantages below compared with prior art：（1）The many thienyl D- π-A type dyes of triphen amine（TTPA-
NUIST）Synthetic route is simple, with low cost, can obtain higher yield.（2）The many thienyl D- π-A type dyes of triphen amine
（TTPA-NUIST）Electron donor on 5 of thienyl can further be replaced, facilitate the later stage to carry out structural modification, hold
Easily realize the ultraviolet spectral absorption to near-infrared region；（3）The many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）
The molar extinction coefficient of near ultraviolet band is higher, therefore can significantly improve pair of battery as sensitizer in solar cells
The opto-electronic conversion performance of ultraviolet light.（4）Due to many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）Chemical property
It is stable, many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）It is stable in properties in cell assembling processes, it is difficult desorption
It is attached, it is favorably improved battery bulk life time.The present invention for triphen amine dyestuff MOLECULE DESIGN with preparation provide new method and
New way, while being provided for many thienyl D- π-A type dyes of triphen amine in the application of DSSC reliable
Technical support.
Brief description of the drawings
Fig. 1 is the synthetic route chart of many thienyl triphenylamine compounds of the invention；
Fig. 2 is the electrospray ionization mass spectrum figure of many thienyl triphenylamine compounds of the invention；
Fig. 3 is many thienyl triphenylamine compounds of the invention1H NMR spectras；
Fig. 4 is the uv-visible absorption spectra and fluorescence emission spectrogram of compound of many thienyl triphenylamine compounds of the invention；
Fig. 5 is the structural representation that embodiment 4 is prepared；
Fig. 6 is what the DSSC that embodiment 4 is prepared was measured under standard analog sunshineJ-VIt is bent
Line.
In Fig. 5,1- dyestuffs, 2-TiO2Electrode, 3-Pt is to electrode, 4- electrolyte, 5- cover glasses.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine（TTPA-Br）It is according to documentJounal of Medicinal Chemistry,2012, 55, made from 9562-9575；5-thiophene acetylene-2-formic acid is according to text
OfferMacromolecules, 2002, 35, made from 5782-5788.
Prepare embodiment 1
Under argon gas protection, 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) is added in three-necked bottle
Amine（TTPA-Br）(57.0 mg, 0.1 mmol) and 5-thiophene acetylene-2-formic acid (45.60 mg, 0.30 mmol) dissolve
Deaerated 15 minutes with nitrogen displacement in tetrahydrofuran (30 mL) and triethylamine (5 mL).Then, under nitrogen protection in
Solution adds Pd (PPh3)4(11.56 mg, 0.01 mmol) and CuI (1.90 mg, 0.01 mmol), and stirred at 40 DEG C
Mix 48 hours.Reaction process is detected with TLC.After reaction terminates, vacuum distillation removes solvent, and residue is purified with column chromatography, washed
De- liquid is 9 by volume ratio:1 dichloromethane and methanol composition, finally in dichloromethane and methanol（Volume ratio：9:1）It is middle heavy
Crystallization, obtains the mg of buff product TTPA-NUIST 41.0, yield 64%（On the basis of TTPA-Br）.Mass spectrometric data
(MALDI–Tof): Calcd for C37H23NO2S4, 641.06; found, 639.92, {[M–H]–, referring to Fig. 2；
Proton NMR spectrum data1H NMR (CDCl3, 400 MHz): δ, [ppm]: 7.75 (d, J = 3.9 Hz, 1H),
7.53 (d, J = 8.6 Hz, 4H), 7.49 (d, J = 8.6 Hz, 2H), 7.29 (d, J = 3.8 Hz, 1H),
7.24-7.26 (m, 1H), 7.23 (d, J = 3.9 Hz, 1H), 7.15-7.19 (m, 8H), 7.07 (m, 2H),
6.84 (d, J =7.9 Hz, 2H), referring to Fig. 3.Dyestuff TTPA-NUIST structural formula is as shown in Figure 1.
Prepare embodiment 2
Under argon gas protection, 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine is added in three-necked bottle
（TTPA-Br）(57.0 mg, 0.1 mmol) and 5-thiophene acetylene-2-formic acid (56.0 mg, 0.50 mmol) are dissolved in
Deaerated 15 minutes with nitrogen displacement in tetrahydrofuran (20 mL) and triethylamine (3mL).Then, under nitrogen protection to middle solution
Add Pd (PPh3)4(23.12 mg, 0.02 mmol) and CuI (3.80 mg, 0.02 mmol), and stirred at 50 DEG C
24 hours.Reaction process is detected with TLC.After reaction terminates, vacuum distillation removes solvent, and residue is purified with column chromatography, elutes
Liquid is 10 by volume ratio:1 dichloromethane and methanol composition, finally in dichloromethane and methanol（Volume ratio：6:1）Middle heavy knot
Crystalline substance, obtains the mg of buff product TTPA-NUIST 38.0, yield 59%（On the basis of TTPA-Br）.
Effect example 1
Take prepare the dyestuff TTPA-NUIST for preparing in embodiment 1 or 2 be configured to 0.02 mM TTPA-NUIST it is molten
Liquid, solvent is CHCl3.The ultraviolet-visible absorption spectroscopy of dye solution is measured by Shimadzu UV -3600 spectroscopes, record
Spectral absorption between 300-700 nm.TTPA-NUIST ultraviolet-visible spectrum is referring to Fig. 4.300-480 nm ultraviolet-visible
The electric charge that spectral absorption is mostly come between π-π * transition and intramolecular electron donor and acceptor inside each group of intramolecular turns
Move (ICT), illustrate the electric field presence of intramolecular pole, electric charge transfer can be realized under optimum conditions.From ultraviolet-visible absorption spectroscopy
It can also be seen that many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）In the molar extinction coefficient of near ultraviolet band
It is higher, therefore can significantly improve the opto-electronic conversion performance to black light of battery as sensitizer in solar cells.
The fluorescence emission spectrum of dye solution is surveyed at room temperature by a Perkin Elmer LS55 spectrophotometer
It is fixed.It can be seen that, under 370 nm exciting, TTPA-NUIST has a stronger absworption peak in 450-650 nm, illustrates
The dyestuff has preferably yellow fluorescence performance.
Embodiment 3（It is prepared by light anode）
FTO sheet glass and TiO2Slurry is bought from DaLian, China seven-colour-light Science and Technology Ltd..The sheet resistance of FTO glass
For 15 Ω cm–2.Before use, FTO sheet glass ultrasound 30 minutes in detergent solution are washed with water and ethanol, then soaked
In 40 mM TiCl4In the aqueous solution, soaked 30 minutes at 70 DEG C, then washed with water and ethanol.
TiO is prepared by screen printing technique2Nano-crystalline photoelectric pole.TiO2Slurry is by 20 nm TiO2Nano particle, second
Base cellulose (being used as binding agent) and α-terpinol (as solvent) composition.TiO2After being screen-printed on FTO sheet glass
Sintered 1 hour at 500 DEG C.1.0 × 1.0 cm2 TiO2The thickness of film is 12 μm.Gained TiO2Electrode uses TiCl again4
Processing, soaks 30 minutes at 70 DEG C, and is sintered 30 minutes at 450 DEG C.When being cooled to 80 DEG C, by gained TiO2 electrodes
It is immersed in 0.4 mM dyestuffs (TTPA-NUIST) solution, solvent uses volume ratio for 3:2 CHCl3With EtOH mixed solutions,
Soak time will be more than 24 hours.TiO is washed with acetonitrile2Electrode, washes away and do not adsorb in TiO2Dyestuff on electrode, that is, be made
Light anode.
Embodiment 4（The many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）The DSSCs solar cells of sensitization
The preparation of device）
Heat-sealing film and Pt electrodes are bought from DaLian, China seven-colour-light Science and Technology Ltd..It is used as by heating between the two poles of the earth
The heat-sealing film of pad, has adsorbed the TiO of dyestuff 12Electrode 2（That is it is prepared by light anode, embodiment 3）One is assembled into electrode 3 with Pt
The battery of the sandwich type of individual sealing.Electrolyte 4 is dripped at the hole to electrode, electrolyte is injected into by vacuum backfill
In battery.Finally, Pt is sealed to the hole on electrode with heat-sealing film and cover glass 5 (0.1mm is thick).Being injected into the electrolyte of battery is
Containing 0.6 M 1- butyl -3- methylimidazole salt compounded of iodine, 50 mM LiI, 30 mM I2,0.5 M tert .-butylpyridines and 0.1 M sulphur
The solution of cyanic acid guanidine, solvent is that (volume ratio is 85 for acetonitrile and valeronitrile mixture:15).Lastblock is pasted at every piece of back side to electrode
Aluminium foil, just obtains many thienyl D- π-A type dyes of triphenylamine class（TTPA-NUIST）The DSSCs solar cell devices of sensitization.
The structural representation of made device is as shown in Figure 5.
DSSCs solar cell device performance tests part uses Newport solar battery efficiency test systems, passes through
The measure of J-V curves, find out short circuit current flow (Jsc) and open-circuit voltage (Voc), calculate due to being lost caused by the resistance of device
Fill factor, curve factorFF [FF=(JV)max/JscVoc] and represent battery main performance Parameter Energy conversion efficiency（）.
As a result it is as shown in Figure 6, it can be seen that many thienyl D- π-A type dyes of triphenylamine class（TTPA-NUIST）Sensitization
DSSCs solar cell devices are under a standard analog sunshine：Short circuit current flow (Jsc) it is 11.31 mA/cm2, open circuit electricity
Pressure (Voc) it is 0.701V, fill factor, curve factorFFFor 63.30%, energy conversion efficiency（）For 5.02%.Above-mentioned the performance test results table
It is bright, many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）The DSSCs solar cell devices of sensitization have higher
Electricity conversion.Due to many thienyl D- π-A type dyes of triphen amine（TTPA-NUIST）Stable chemical nature, triphen amine
Many thienyl D- π-A type dyes（TTPA-NUIST）It is stable in properties in cell assembling processes, De contamination is difficult, the battery is overall
Last a long time.
Claims (9)
1. a kind of many thienyl triphenylamine compounds, it is characterised in that the structure of many thienyl triphenylamine compounds
Formula is as follows：
。
2. the preparation method of many thienyl triphenylamine compounds described in claim 1, it is characterised in that comprise the following steps：
Under argon gas protection, 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine and 5-acetylene are added in three-necked bottle
Base-2-formic acid of thiophene, after being dissolved using tetrahydrofuran and triethylamine as solvent, is deaerated 15-30 minutes with nitrogen displacement；Then, exist
Pd (PPh are added into solution under nitrogen protection3)4And CuI, and stirred 24-48 hours at 35-55 DEG C, purifying, produce described
Many thienyl triphenylamine compounds.
3. preparation method according to claim 2, it is characterised in that 4- (5- bromothiophene bases the phenyl)-N, N- bis-
The mol ratio of (4- thienyls phenyl) amine and 5-thiophene acetylene-2-formic acid is 1:2-1:5；The consumption of the tetrahydrofuran is every
100 milligrams of 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine add 5-100 milliliters；The use of the triethylamine
Measure and add 2-20 milliliters for every 100 milligrams of 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine；The Pd
(PPh3)4Mol ratio with 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine is 0.01:1-0.2:1；It is described
Pd(PPh3)4Mol ratio with CuI is 1:1.
4. the preparation method according to Claims 2 or 3, it is characterised in that 4- (5- bromothiophene bases the phenyl)-N, N-
The mol ratio of two (4- thienyls phenyl) amine and 5-thiophene acetylene-2-formic acid is 1:3；The consumption of the tetrahydrofuran is
0.1mmol 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine adds 30 milliliters；The consumption of the triethylamine
5 milliliters are added for 0.1mmol 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine；Pd (the PPh3)4With
The mol ratio of 4- (5- bromothiophene bases phenyl)-N, N- bis- (4- thienyls phenyl) amine is 1:10；Pd (the PPh3)4With CuI's
Mol ratio is 1:1.
5. the preparation method according to Claims 2 or 3, it is characterised in that the purge process is purified using column chromatography, is washed
De- agent uses dichloromethane and methanol mixed solution, collects after eluent, concentrate drying produces many thienyl triphen amines
Compound；The volume ratio of the dichloromethane and methanol is 10:0.5-10:1.5.
6. preparation method according to claim 5, it is characterised in that after the eluent concentrate drying, using dichloromethane
The mixed solvent of alkane and methanol is recrystallized；The volume ratio of dichloromethane and methanol is in the recrystallization mixed solvent：5:
1-15:1。
7. preparation method according to claim 5, it is characterised in that the volume of dichloromethane and methanol in the eluant, eluent
Than for 9:1；The stationary phase of the column chromatography uses the silica gel of 200-300 mesh.
8. application of many thienyl triphenylamine compounds in DSSC described in claim 1.
9. application according to claim 8, it is characterised in that the light anode of the DSSC use with
It is prepared by lower step：
（1）Prepare dye solution：Many thienyl triphenylamine compounds are dissolved in the mixed solution of chloroform and ethanol
In；The concentration of many thienyl triphenylamine compounds is 0.4mmol/L；The volume ratio of the chloroform and ethanol is 3:
2；
（2）It is prepared by light anode：By TiO2Electrode is placed in step（1）24-48h is soaked in the dye solution prepared, is produced.
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