CN109575005A - 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents and preparation method thereof - Google Patents

4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents and preparation method thereof Download PDF

Info

Publication number
CN109575005A
CN109575005A CN201811426254.4A CN201811426254A CN109575005A CN 109575005 A CN109575005 A CN 109575005A CN 201811426254 A CN201811426254 A CN 201811426254A CN 109575005 A CN109575005 A CN 109575005A
Authority
CN
China
Prior art keywords
formula
compound
alkylbenzene
bithiophene
light
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811426254.4A
Other languages
Chinese (zh)
Other versions
CN109575005B (en
Inventor
伍致生
郭旺军
张�杰
宋新潮
刘亚东
王户生
周继华
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian Modern Chemistry Research Institute
Original Assignee
Xian Modern Chemistry Research Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian Modern Chemistry Research Institute filed Critical Xian Modern Chemistry Research Institute
Priority to CN201811426254.4A priority Critical patent/CN109575005B/en
Publication of CN109575005A publication Critical patent/CN109575005A/en
Application granted granted Critical
Publication of CN109575005B publication Critical patent/CN109575005B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero 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
    • C09B57/00—Other synthetic dyes of known constitution
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
    • H01G9/2022—Light-sensitive devices characterized by he counter electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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

Abstract

The invention discloses a kind of 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents and preparation method thereof, and the structural formula of the light-sensitive coloring agent is as follows:R in formula1Represent C1~C10Alkyl；D is thiocarbamide triphenylamine electron donor.The present invention introduces alkylbenzene in 4 and 4 ' two positions of bithiophene bridge chain, it can reach the double effects widened pure organic photosensitive dyestuff absorption band range and inhibit intermolecular reunion: on the one hand, alkylbenzene can further improve the electron rich performance of bithiophene bridge chain, transmitting conducive to electronics from from donor to receptor, to widen the absorption band range of dyestuff；On the other hand, alkylbenzene has certain steric hindrance, and the reunion between dye molecule can be effectively suppressed.4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents can be used for preparing solar battery, and because of its ruthenium without precious metal, preparation cost is low, and purification process is simple, has broad application prospects.

Description

4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents and its preparation Method
Technical field
The invention belongs to organic dyestuff technical fields, and in particular to using thiocarbamide triphenylamine as electron donor, with 4,4 '-two (alkylbenzene) bithiophene is bridge chain and the organic dyestuff for connecting electron-withdrawing group.
Background technique
The challenge that energy crisis and environmental pollution propose Global Sustainable Development increasingly sharpens, and exploitation cleaning is renewable new The energy has become the great direction in the planning of countries in the world.Compared with fossil fuel, nuclear energy, water energy, wind energy etc., solar energy tool There is unique advantage, because its total amount is big, safety and is not limited by geographical conditions.It is successfully developed from AT&T Labs, the U.S. in 1954 First practical silicon solar cell and for since artificial satellite power supply, solar battery research to achieve huge progress, Third generation solar cell is developed to.Wherein, the manufacturing process of dye-sensitized solar cells (DSSCs) is simple, cost It is low, incident photon-to-electron conversion efficiency is high, be a research hotspot of current area of solar cell.
The component of DSSCs includes light anode, light-sensitive coloring agent, electrolyte and to electrode, and light-sensitive coloring agent is mainly responsible for and catches Obtain photon and to TiO2Conduction band injects the important function such as electronics, therefore its performance directly affects the photoelectric conversion effect of DSSCs Rate.Currently, having reached 11% by ruthenium-complex compound DSSCs incident photon-to-electron conversion efficiency of representative of N719, recently, zinc-porphyrin is utilized The DSSCs incident photon-to-electron conversion efficiency that complex compound and triphenylamine organic dyestuff are sensitized altogether has reached 13%.However, ruthenium-complex compound is containing expensive Metal Ru, resource is limited, price is high, in addition, zinc-porphyrin complex complex synthetic route, these all limit ruthenium-complex compound With application of the zinc-porphyrin complex in DSSCs.
As the contenders of metal-complex light-sensitive coloring agent, pure organic photosensitive dyestuff receives more and more passes Note, this kind of dyestuff have the advantage that (1) compared with metal-complex light-sensitive coloring agent, their molar absorption coefficient is bigger, Thus light capture rate is higher；(2) flexible structure is changeable, this is provided greatly just for functional objective light-sensitive coloring agent MOLECULE DESIGN Benefit；(3) at low cost, it pollutes small.But the extinction bands of a spectrum narrow range of pure organic photosensitive dyestuff, molecule are easy accumulation and reunite, institute It is not high with the incident photon-to-electron conversion efficiency of usual this kind of light-sensitive coloring agent.Thus, how effectively to widen the suction of pure organic photosensitive dyestuff Receive the key problem that reunion between bands of a spectrum and inhibition dye molecule is current DSSCs development field concern.
Pure organic photosensitive dye molecule usually consists of three parts, i.e., electron donor (D), conjugated bridge chain (π) and electronics by Body (A).Feature in such a structure is conducive to realize that performance optimizes by the modification and adjustment of molecular structure.Research hair Existing, the absorption band range of light-sensitive coloring agent can be widened by extending conjugated bridge chain, but simply extend conjugated bridge chain to a certain degree On can aggravate the intermolecular reunion of light-sensitive coloring agent.
Summary of the invention
Technical problem to be solved by the present invention lies in above-mentioned organic photosensitive dyestuff is overcome, a kind of absorption spectra is provided Wide with range, not easy to reunite 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents, and provided for the dyestuff A kind of preparation method easy to operate, high income.
Technical solution used by solution above-mentioned technical problem is that the structural formula of the light-sensitive coloring agent is as follows:
In formula, R1Represent C1~C10Alkyl；D is represented with flowering structure:
In formula, R2Represent C1~C10Alkyl.
The preferred R of the present invention1Represent C1~C10Alkyl, D are representedR2Represent C6Alkyl (just oneself Base).
Above-mentioned 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent the preparation method comprises the following steps:
1,1 compound of preparation formula
Using the volume ratio of tetrahydrofuran and water for 5:1 mixed liquor as solvent, by 3 bromo thiophene, C1~C10To alkylbenzene Boric acid, tetrakis triphenylphosphine palladium, potassium carbonate are 1:1~1.2:0.03~0.05:1.5~2.0,60~80 DEG C of reactions in molar ratio 8~12 hours, product is isolated and purified, obtains 1 compound of formula, chemical equation is as follows:
R in formula1Represent C1~C10Alkyl.
2,2 compound of preparation formula
Using tetrahydrofuran as solvent, by 1 compound of formula and butyl lithium, N, N, N, N- tetramethylethylenediamine (TMEDA) massage , than being 1:1.0~1.2:1.0~1.2, -78~-60 DEG C are reacted 0.5~1 hour for you, and it is small to be warming up to 50~60 DEG C of reactions 0.5~1 When, it is cooled to -78~-60 DEG C, is added copper chloride, the molar ratio of 1 compound of formula and copper chloride is 1:1.0~1.2, reaction 1~2 Hour, product is isolated and purified, 2 compound of formula is obtained, chemical equation is as follows:
3,3 compound of preparation formula
Using dichloroethanes as solvent, by 2 compound of formula, n,N-Dimethylformamide, phosphorus oxychloride be in molar ratio 1:1~ 1.2:1~1.2,0~60 DEG C is reacted 6~8 hours, is isolated and purified product, is obtained 3 compound of formula, chemical equation is such as Under:
4,4 compound of preparation formula
Using n,N-Dimethylformamide as solvent, by 3 compound of formula and N- bromo-succinimide be in molar ratio 1:1~ It is reacted 4~8 hours at 1.1,70~90 DEG C, isolates and purifies product, obtain 4 compound of formula, chemical equation is as follows:
5,6 compound of preparation formula
Using the volume ratio of tetrahydrofuran and water for 5:1 mixed liquor as solvent, by donor shown in 4 compound of formula and formula 5 Borate, four (triphenyl phosphorus) palladiums, potassium carbonate are 1:1~1.2:0.03~0.05:1.5~2.0 in molar ratio, and 60~80 DEG C anti- It answers 8~12 hours, isolates and purifies product, obtain 6 compound of formula, chemical equation is as follows:
D is represented with flowering structure in formula:
Wherein R2For C1~C10Alkyl.
6,4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents are prepared
Using glacial acetic acid as solvent, by 6 compound of formula, cyanoacetic acid, ammonium acetate be in molar ratio 1:1~1.2:1.5~ 2.0,100~120 DEG C are reacted 3~5 hours, are isolated and purified product, are obtained 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphens Amine light-sensitive coloring agent, chemical equation are as follows:
Of the invention 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent rutheniums without precious metal, preparation It is at low cost, and purification process is simple.Alkylbenzene is introduced in the 4 of bithiophene and 4 ' positions, can further improve the richness of bithiophene bridge chain Electronic Performance widens the absorption band range of dyestuff, improves the short circuit of device to be conducive to transmitting of the electronics from donor to receptor Current density；In addition, alkylbenzene may also suppress the compound of reunion between dye molecule and injection electronics and electrolyte, thus sharp The photoelectricity turn that can more effectively improve device is improved while the higher open-circuit voltage of acquisition, short-circuit current density and open-circuit voltage Change efficiency.Gained 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent is used to prepare the light of solar battery Electrotransformation efficiency is higher than N719 dye-sensitized solar cells incident photon-to-electron conversion efficiency under the same terms, before wide application Scape.
Specific embodiment
With embodiment, the present invention is described in more detail below, but protection scope of the present invention is not limited only to these implementations Example.
Embodiment 1
By taking 4,4 '-two following (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents of preparation structure formula as an example, The preparation method comprises the following steps:
1,1 compound of preparation formula
100mL tetrahydrofuran and 20mL water are added into three neck round bottom flask, adds 6.52g (0.04mol) 3- bromine thiophene Pheno, 8.54g (0.048mol) are to butyl phenyl boric acid, 2.31g (0.002mol) tetrakis triphenylphosphine palladium, 11.04g (0.08mol) Potassium carbonate, 70 DEG C are reacted 10 hours, and room temperature, liquid separation are down to, and organic phase is dried, filtered with anhydrous magnesium sulfate, and solvent is evaporated off, remaining Object uses column chromatography (eluant, eluent is petroleum ether), obtains 1 compound 7.44g of formula, yield 86%.Its chemical equation is such as Under:
2,2 compound of preparation formula
100mL tetrahydrofuran is added into three neck round bottom flask, adds 1 compound of 5.2g (0.024mol) formula, 3.35g (0.029mol) N, N, N, N- tetramethylethylenediamine (TMEDA), is cooled to -78 DEG C, be added dropwise 11.5mL butyl lithium (0.029mol, 2.5M), 60 DEG C are warming up to react 1 hour, is cooled to -78 DEG C, adds 4.5g (0.029mol) copper chloride, is reacted 2 hours, mistake Filter, is evaporated off solvent, and residue obtains 2 compound 2.79g of formula, yield 54% with column chromatographic purifying (eluant, eluent is petroleum ether).Its Chemical equation is as follows:
3,3 compound of preparation formula
At 0 DEG C, 60mL dichloroethanes is added into three neck round bottom flask, adds 2 chemical combination of 2.58g (0.006mol) formula Object, 0.53g (0.0072mol) n,N-Dimethylformamide, 1.11g (0.0072mol) phosphorus oxychloride, 60 DEG C are reacted 8 hours, are stopped It only reacts, is down to room temperature, and 60mL water is added, liquid separation, organic phase is dry with anhydrous magnesium sulfate, and solvent, residue column is evaporated off Chromatographic purifying (eluant, eluent is petroleum ether: ethyl acetate=10:1 mixed liquor), is evaporated off eluant, eluent, obtains 3 compound of formula 2.42g, yield 88%.Its chemical equation is as follows:
4,4 compound of preparation formula
40mL n,N-Dimethylformamide is added into three neck round bottom flask, adds the change of 2.29g (0.005mol) formula 3 Object, 0.89g (0.005mol) N- bromo-succinimide (NBS) are closed, is reacted 6 hours at 80 DEG C, is down to room temperature, is transferred to beaker In, 60mL methylene chloride is added into reaction solution and 60mL saturated sodium bicarbonate aqueous solution, liquid separation, water phase are extracted with dichloromethane Twice, merge organic phase, it is dry with anhydrous magnesium sulfate, be evaporated off solvent, residue with column chromatographic purifying (eluant, eluent is petroleum ether: Ethyl acetate=10:1 mixed liquor), eluant, eluent is evaporated off, obtains 4 compound 2.02g of formula, yield 75%.Its chemical reaction equation Formula is as follows:
5,6 compound of preparation formula
40mL tetrahydrofuran and 8mL water are added into three neck round bottom flask, adds 4 chemical combination of 2.14g (0.004mol) formula Object, 5 compound of 4.09g (0.0048mol) thiocarbamide triphenylamine borate formula, 0.23g (0.0002mol) tetrakis triphenylphosphine palladium, 1.1g (0.008mol) potassium carbonate, 70 DEG C are reacted 10 hours, are down to room temperature, liquid separation, organic phase is dry with anhydrous magnesium sulfate, mistake Filter, is evaporated off solvent, residue uses column chromatography (eluant, eluent is petroleum ether: ethyl acetate=4:1 mixed liquor), obtains formula 6 Compound 3.45g, yield 73%.Its chemical equation is as follows:
6,4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents are prepared
20mL glacial acetic acid is added into three neck round bottom flask, adds 6 compound of 2.36g (0.002mol) formula, 0.2g (0.0022mol) cyanoacetic acid, 0.2g (0.004mol) ammonium acetate, 110 DEG C are reacted 4 hours, are down to room temperature, are added into flask 20mL methylene chloride and 20mL water, liquid separation, water phase are extracted with dichloromethane twice, merge organic phase, dry with anhydrous magnesium sulfate, It is evaporated off solvent, (eluant, eluent is petroleum ether to residue: ethyl acetate=3:1 mixed liquor, separately plus mixing liquid with column chromatographic purifying The acetic acid of product 1%), eluant, eluent is evaporated off, obtains 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent 1.62g, Yield 65%.Its chemical equation is as follows:
The spectral data of 4,4 '-two prepared (alkylbenzene) bithiophene bridging light-sensitive coloring agents are as follows:1H NMR (400MHz, CDCl3, TMS) and δ (ppm): 8.36 (s, 1H), 7.45 (s, 1H), 7.34-7.28 (m, 4H), 7.27-7.25 (m, 3H), 7.18 (d, J=9.0Hz, 2H), 7.13 (d, J=8.0Hz, 2H), 7.06 (d, J=9.0Hz, 2H), 6.99-6.96 (m, 4H), 6.89 (d, J=8.0Hz, 2H), 4.27 (t, J=8.0Hz, 4H), 4.18 (t, J=8.0Hz, 4H), 2.69 (t, J=8.0Hz, 2H), 2.61 (t, J=8.0Hz, 2H), 1.84-1.80 (m, 4H), 1.75-1.71 (m, 4H), 1.68-1.65 (m, 2H), 1.63-1.61 (m, 2H), 1.44-1.40 (m, 6H), 1.37-1.31 (m, 12H), 1.28-1.23 (m, 8H), 0.97 (t, J=8.0Hz, 3H), 0.93 (t, J=8.0Hz, 3H), 0.89 (t, J=7.0Hz, 6H), 0.82 (t, J=7.0Hz, 6H)13C NMR(100MHz, CDCl3) δ (ppm): 169.45,167.75,155.45,148.03,147.27,146.30,144.52,142.91,142.34, 140.71,139.18,133.11,133.06,132.76,131.37,130.70,129.70,129.44,129.14,128.90, 128.82,128.58,126.54,120.83,120.67,116.28,109.63,106.27,96.01,44.94,44.73, 35.47,35.42,33.50,33.43,31.48,31.42,27.94,27.82,26.58,26.48,22.55,22.49, 22.47,22.42,14.02,14.00,13.97,13.97.
Prepared 4,4 '-two (alkylbenzene) bithiophene bridging light-sensitive coloring agents are used to prepare dye-sensitized solar cells, It is specific the preparation method is as follows:
FTO electro-conductive glass piece (14 Ω/sq, it is seen that light transmittance > 90% in light area) is cleaned by ultrasonic in the following order: cleaning Then agent, acetone, deionized water apply one layer of TiO thereon with method for printing screen2Slurry is received by following procedure sintering preparation Meter Duo Kong TiO2Working electrode: 300 DEG C of burning 5min, 400 DEG C of burning 5min, 450 DEG C of burning 30min.Wait be cooled to room temperature, gained is received Meter Duo Kong TiO2Working electrode immerses 0.4mmol/L4, in the ethanol solution of 4'- bis- (alkylbenzene) bithiophene bridging light-sensitive coloring agent, It is sensitized 12h at room temperature.Platinum slurry is brushed in FTO electro-conductive glass on piece screen printing, and is sintered 15min at 400 DEG C, obtained pair Electrode.Sealant (25 μm, Surlyn 1702) is placed in the TiO among two electrodes by dye sensitization2Light anode and to electrode group The DSSCs battery for dressing up encapsulation, using vacuum-suck-back method by electrolyte solution by being filled into battery to the aperture on electrode In, the composition of electrolyte solution are as follows: 0.6mol/L iodate 1- butyl -3- methylimidazole (BMII), 0.1mol/L LiI, 0.03mol/L I2, 0.5mol/L 4- tert .-butylpyridine and 0.1mol/L sulphur nitrile guanidine acid acetonitrile solution.Finally, fill orifice is used Coverslip and sealant sealing, are prepared into dye-sensitized solar cells.
Density of photocurrent-voltage (J-V) characteristic curve of battery measures under AM 1.5G simulated solar light intensity, simulator For 300W xenon lamp (94022A, Newport Co., the U.S.), incident intensity is calibrated to 100mW/ with standard silicon solar cell cm2, computer-controlled Data source table (Keithley 2400) acquisition of Current density-voltage characteristic curve data, the work of battery Making area is 0.16cm2.Electricity prepared by 4,4 '-two (alkylbenzene) bithiophene bridging light-sensitive coloring agents using the embodiment of the present invention 1 The incident photon-to-electron conversion efficiency in pond is 8.12%, short circuit current 16.4mA/cm2, open-circuit voltage 786mV, fill factor 0.63. The incident photon-to-electron conversion efficiency for measuring N719 sensitizing dyestuff solar battery in the method is 7.82%, short circuit current 16.6mA/ cm2, open-circuit voltage 746mV, fill factor 0.63.Contrast test the result shows that, be prepared into using the embodiment of the present invention 1 The incident photon-to-electron conversion efficiency of solar battery is higher than N719 dye-sensitized solar cells incident photon-to-electron conversion efficiency under the same terms.
Embodiment 2
By taking 4,4 '-two following (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents of preparation structure formula as an example, The preparation method comprises the following steps:
In 1 chemical procedure 1 of preparation formula of embodiment 1, it is used to butyl phenyl boric acid with equimolar to methylbenzene Boric acid replacement, other steps of the step are same as Example 1, and other steps are identical as corresponding embodiment, are prepared into 4,4 '- Two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents.
It is according to the method for embodiment 1 that 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamines of the present embodiment are photosensitive Dyestuff is prepared into dye-sensitized solar cells, after tested its incident photon-to-electron conversion efficiency be 7.97%, short circuit current 16.6mA/ cm2, open-circuit voltage 774mV, fill factor 0.62.Its incident photon-to-electron conversion efficiency is too higher than N719 sensitizing dyestuff under the same terms Positive energy cell photoelectric transformation efficiency.
Embodiment 3
By taking 4,4 '-two following (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents of preparation structure formula as an example, The preparation method comprises the following steps:
In 1 chemical procedure 1 of preparation formula of embodiment 1, it is used to butyl phenyl boric acid with equimolar to Kui Ji benzene Boric acid replacement, other steps of the step are same as Example 1, and other steps are identical as corresponding embodiment, are prepared into 4,4 '- Two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents.
It is according to the method for embodiment 1 that 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamines of the present embodiment are photosensitive Dyestuff is prepared into dye-sensitized solar cells, after tested its incident photon-to-electron conversion efficiency be 8.00%, short circuit current 16.2mA/ cm2, open-circuit voltage 796mV, fill factor 0.62.Its incident photon-to-electron conversion efficiency is too higher than N719 sensitizing dyestuff under the same terms Positive energy cell photoelectric transformation efficiency.

Claims (2)

  1. One kind 4,4 '-two 1. (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent, it is characterised in that the light-sensitive coloring agent Structural formula is as follows:
    In formula, R1Represent C1~C10Alkyl；D is represented with flowering structure:
    In formula, R2Represent C1~C10Alkyl.
  2. 2. a kind of preparation side of 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agent described in claim 1 Method, it is characterised in that steps are as follows:
    (1) 1 compound of preparation formula
    Using the volume ratio of tetrahydrofuran and water for 5:1 mixed liquor as solvent, by 3 bromo thiophene, C1~C10To alkylbenzene boron Acid, tetrakis triphenylphosphine palladium, potassium carbonate are 1:1~1.2:0.03~0.05:1.5~2.0,60~80 DEG C of reactions 8 in molar ratio ~12 hours, product is isolated and purified, obtains 1 compound of formula；
    R in formula1Represent C1~C10Alkyl；
    (2) 2 compound of preparation formula
    Using tetrahydrofuran as solvent, by 1 compound of formula and butyl lithium, N, N, N, N- tetramethylethylenediamine is 1:1.0 in molar ratio ~1.2:1.0~1.2, -78~-60 DEG C are reacted 0.5~1 hour, are warming up to 50~60 DEG C and are reacted 0.5~1 hour, be cooled to - 78~-60 DEG C, copper chloride is added, the molar ratio of 1 compound of formula and copper chloride is 1:1.0~1.2, is reacted 1~2 hour, separation Purified product obtains 2 compound of formula；
    (3) 3 compound of preparation formula
    In molar ratio it is 1:1~1.2 by 2 compound of formula, n,N-Dimethylformamide, phosphorus oxychloride using dichloroethanes as solvent: 1~1.2,0~60 DEG C is reacted 6~8 hours, is isolated and purified product, is obtained 3 compound of formula；
    (4) 4 compound of preparation formula
    It is in molar ratio 1:1~1.1 by 3 compound of formula and N- bromo-succinimide using n,N-Dimethylformamide as solvent, It is reacted 4~8 hours at 70~90 DEG C, isolates and purifies product, obtain 4 compound of formula；
    (5) 6 compound of preparation formula
    Using the volume ratio of tetrahydrofuran and water for 5:1 mixed liquor as solvent, by donor boric acid shown in 4 compound of formula and formula 5 1:1~1.2:0.03~0.05:1.5~2.0 reacts in molar ratio for ester, four (triphenyl phosphorus) palladiums, potassium carbonate, 60~80 DEG C of reactions 8~12 hours, product is isolated and purified, obtains 6 compound of formula；
    D is represented with flowering structure in formula:
    Wherein R2For C1~C10Alkyl；
    (6) 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents are prepared
    It is in molar ratio 1:1~1.2:1.5~2.0 by 6 compound of formula, cyanoacetic acid, ammonium acetate using glacial acetic acid as solvent, 100 ~120 DEG C are reacted 3~5 hours, isolate and purify product, it is photosensitive to obtain 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamines Dyestuff.
CN201811426254.4A 2018-11-27 2018-11-27 4,4' -di (alkylbenzene) bithiophene bridged thiourea triphenylamine photosensitive dye and preparation method thereof Active CN109575005B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811426254.4A CN109575005B (en) 2018-11-27 2018-11-27 4,4' -di (alkylbenzene) bithiophene bridged thiourea triphenylamine photosensitive dye and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811426254.4A CN109575005B (en) 2018-11-27 2018-11-27 4,4' -di (alkylbenzene) bithiophene bridged thiourea triphenylamine photosensitive dye and preparation method thereof

Publications (2)

Publication Number Publication Date
CN109575005A true CN109575005A (en) 2019-04-05
CN109575005B CN109575005B (en) 2021-06-15

Family

ID=65924464

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811426254.4A Active CN109575005B (en) 2018-11-27 2018-11-27 4,4' -di (alkylbenzene) bithiophene bridged thiourea triphenylamine photosensitive dye and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109575005B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100099A (en) * 2019-12-03 2020-05-05 西安近代化学研究所 Triphenylamine co-sensitizer with phenyl as tail end bridge chain and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014047224A (en) * 2012-08-29 2014-03-17 Ritsumeikan Method for producing organic coloring matter mk-2
CN103992658A (en) * 2014-05-15 2014-08-20 陕西师范大学 Thiourea functionalized triphenylamine organic dye and application thereof
JP2017076648A (en) * 2015-10-13 2017-04-20 関東天然瓦斯開発株式会社 Fully organic dye compound having heterocyclic linker group for dye-sensitized photoelectric conversion element, and photoelectric conversion element using the same
CN108503654A (en) * 2018-04-28 2018-09-07 陕西师范大学 The thiocarbamide triphen amine dye sensitizing agent of Thienopyrroles diketone modification

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014047224A (en) * 2012-08-29 2014-03-17 Ritsumeikan Method for producing organic coloring matter mk-2
CN103992658A (en) * 2014-05-15 2014-08-20 陕西师范大学 Thiourea functionalized triphenylamine organic dye and application thereof
JP2017076648A (en) * 2015-10-13 2017-04-20 関東天然瓦斯開発株式会社 Fully organic dye compound having heterocyclic linker group for dye-sensitized photoelectric conversion element, and photoelectric conversion element using the same
CN108503654A (en) * 2018-04-28 2018-09-07 陕西师范大学 The thiocarbamide triphen amine dye sensitizing agent of Thienopyrroles diketone modification

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHOI, H ET AL.: "The impact of an indeno[1,2-b]thiophene spacer on dye-sensitized solar cell performances of cyclic thiourea functionalized organic sensitizers", 《JOURNAL OF MATERIALS CHEMISTRY A》 *
WU, ZS ET AL.: "Cyclic Thiourea/Urea Functionalized Triphenylamine-Based Dyes for High-Performance Dye-Sensitized Solar Cells", 《ORGANIC LETTERS》 *
ZHU,SB ET AL.: "Approach to tune short-circuit current and open-circuit voltage of dye-sensitized solar cells: pi-linker modification and photoanode selection", 《RSC ADVANCES》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100099A (en) * 2019-12-03 2020-05-05 西安近代化学研究所 Triphenylamine co-sensitizer with phenyl as tail end bridge chain and preparation method thereof
CN111100099B (en) * 2019-12-03 2023-04-18 西安近代化学研究所 Triphenylamine co-sensitizer with phenyl as tail-end bridge chain and preparation method thereof

Also Published As

Publication number Publication date
CN109575005B (en) 2021-06-15

Similar Documents

Publication Publication Date Title
CN102532932B (en) Pyrazine-ring-containing organic dyes and preparation method and use thereof
CN102675897B (en) Thiourea/urea aromatic amine dye, as well as preparation method and application thereof
CN109796432A (en) A kind of quick dose and preparation method thereof altogether of alkyl bithiophene -3- fluorobenzene bridged triphenyl amine
CN103554957A (en) Triphenylamine-thiophene organic dyestuff as well as preparation method and application thereof
CN102250484B (en) Method for preparing carbazolyl organic dye used for dye-sensitized solar cells
CN101497746B (en) Organic dye containing thiophen ethylene and dye sensitization solar cell prepared thereby
CN105255209B (en) Thiazolidinethione and triphenylamine light-sensitive dye and preparation method thereof
CN103554958A (en) Dithiophene pyrrole bridge-indoline organic dyes as well as preparation method and application thereof
CN110922392B (en) Carbazole co-sensitizer with phenyl as terminal bridge chain and preparation method thereof
CN105219119B (en) A kind of thiazolone anthracene amine light-sensitive coloring agent and preparation method thereof
CN109575005A (en) 4,4 '-two (alkylbenzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents and preparation method thereof
CN113999217B (en) New compound, preparation method and application thereof as co-sensitizer
CN104559288A (en) Carbazole photosensitive dye as well as preparation method and use of carbazole photosensitive dye
CN101864187B (en) Dye with low energy level difference, intermediate and preparation method and application thereof
CN109777147A (en) A kind of quick dose and preparation method thereof altogether of alkyl bithiophene -2- fluorobenzene bridging carbazole
CN104403351A (en) Organic photosensitive dye based on symmetrical diketopyrrolopyrrole as conjugate bridge
CN109796433A (en) A kind of quick dose and preparation method thereof altogether of alkyl bithiophene -2- fluorobenzene bridged triphenyl amine
CN103834190B (en) Benzothiadiazole-cyanocinnamic acid receptor-containing organic dye and its use in dye-sensitized solar cell
CN111100099B (en) Triphenylamine co-sensitizer with phenyl as tail-end bridge chain and preparation method thereof
CN106810898B (en) Organic dye sensitized dose of the triphen amine of pyrroles's dithione modification and its application
CN103436048B (en) Double-bridge-chain organic dye using thiourea as donor and application thereof
CN109705612A (en) 4,4 '-two (alkoxy benzene) bithiophene bridging thiocarbamide triphenylamine light-sensitive coloring agents of one kind and preparation method thereof
CN102637536A (en) Preparation of solar battery sensitized by utilizing zinc phthalocyanine bisphenol A epoxide derivative
CN113321628A (en) N-type organic dye based on benzothiazol and preparation method and application thereof
CN101967301B (en) Indoline type dyes containing diazosulfide unit and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant