[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN104311543B - A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin - Google Patents

A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin Download PDF

Info

Publication number
CN104311543B
CN104311543B CN201410496693.8A CN201410496693A CN104311543B CN 104311543 B CN104311543 B CN 104311543B CN 201410496693 A CN201410496693 A CN 201410496693A CN 104311543 B CN104311543 B CN 104311543B
Authority
CN
China
Prior art keywords
formula
compound
solvent
tri
arylamine group
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.)
Active
Application number
CN201410496693.8A
Other languages
Chinese (zh)
Other versions
CN104311543A (en
Inventor
韩亮
钟昌健
叶青
李郁锦
高建荣
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.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
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 Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201410496693.8A priority Critical patent/CN104311543B/en
Publication of CN104311543A publication Critical patent/CN104311543A/en
Application granted granted Critical
Publication of CN104311543B publication Critical patent/CN104311543B/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
    • C07D409/02—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
    • C07D409/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • C09B57/02—Coumarine dyes
    • 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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/655—Aromatic compounds comprising a hetero atom comprising only sulfur as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
    • 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
    • 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
    • Y02E10/549—Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

The invention discloses a kind of tri-arylamine group compound containing cumarin and its preparation and application.The tri-arylamine group compound such as formula containing cumarin（Ⅰ）, formula（II）And formula（III）It is shown；Synthetic method of the present invention is：By formula（IVa~IVc）Compound and formula（V）Mix with organic solvent, in the presence of alkali compounds, be heated to reflux the h of stirring reaction 1 ~ 10, after reaction completely, be spin-dried for solvent, residue carries out silica gel column chromatography with eluant, eluent solvent, obtains formula（I~III）The shown tri-arylamine group compound containing cumarin.Tri-arylamine group compound containing cumarin of the present invention can be applied to DSSC as dye sensitizing agent, be dye sensitizing agent screening add it is new can applied material.

Description

A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin
Technical field
The present invention relates to a kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin.
Background technology
DSSC（Dye Sensitized Solar Cell, DSSC）By its low cost, can dim light Generate, Generation, Generator electricity conversion ratio not temperature influence the features such as, pole is hopeful substituted for silicon semiconductor optoelectronic converting member, as the next generation Practical high performance solar cells.Dye sensitizing agent is the crucial knot of decision visible absorption and photoelectric transformation efficiency in DSSC Structure material, modification is easily designed with structure and the features such as processing, low cost, good stability.
The research of Chinese and foreign dyes sensitizer is mainly divided to two classes, and a class is organometallic complex, and typical structure is function The many pyridine ruthenium compounds of property.This kind of dye sensitizing agent absorbs relatively strong in visible region, and redox property is reversible, oxidation stability Height, but ruthenium is relatively costly as rare metal, and its dyestuff absorption spectrum is narrow.Equations of The Second Kind be nonmetallic organic dyestuff, with mole The advantages of absorptivity is high, absorption spectrum is wide and can produce excellent chemical property by structural modification modulation, is to contaminate in recent years Expect the study hotspot of sensitizer.The general structure of traditional nonmetallic organic dye sensitized dose is " donor-pi-conjugated bridge-acceptor " (Donor- π Bridge-Acceptor, D- π-A), according to the difference of donor, existing coumarin type, indoline type, triaryl amine type It is able to design and develops etc. nonmetallic dye sensitizing agent.Conventional acceptor is cyanoacetic acid and rhodanine acetic acid, and in order to enter one Step enhancing acceptor and TiO2Between binding ability, the dye sensitizing agent for also having some non-carboxylic acid acceptors recently is reported.
Triarylamine compounds are the very important organic molecules of a class, with outstanding charge transport properties, it is relatively low from Sonization current potential, hole mobility higher (are typically 10-3~10-4 cm2/ Vs), preferable dissolubility and amorphous film-forming Property, stronger fluorescence property and photostability, be widely used as hole mobile material be applied to organic electroluminescent LED ( OLED), the numerous areas such as organic solar batteries, anaclasis holography, FET.And cumarin and its derivative are made Be in molecule be conjugated electron transporting compound, with excellent fluorescence quantum efficiency, molar absorption coefficient high and Big Stoke displacements, are widely used in the color fluorescence resin of coloring plastic, color fluorescence coating, solar collector, And the high-technology field such as photosensitive material, light-sensitive material, video disc recording material.Due to visible region responsiveness is high, the sun Light irradiation stability inferior is good, and Coumarins dye molecule receives pass extensively as the good dye sensitizing agent of a class development prospect Note.Be introduced into tonka bean camphor structure in triaryl amine donor by the present invention, using triphenylamine cumarin as donor, the aromatic ring conduct containing thiophene Bridged bond, cyanoacetic acid has obtained three triaryl amine Coumarins dye sensitizing agents as acceptor, synthesis.At present, there is no document report The solar cell application of the structure.
The content of the invention
It is an object of the invention to provide a kind of triaryl amine coumarin kind compound preparation and to be applied to dyestuff quick Change solar cell.
Structural formula of the invention is as follows：
It is of the present invention such as formula（I~III）Shown triaryl amine coumarin kind compound can be prepared into accordance with the following methods Arrive：By formula（IVa~ IVc）Compound and formula（V）Mix with organic solvent, in the presence of alkali compounds, be heated to reflux stirring The h of reaction 1 ~ 10 is mixed, after reaction completely, solvent is spin-dried for, residue carries out silica gel column chromatography with eluant, eluent solvent, obtains formula（I~ III）Shown triarylamine compounds containing Coumarins；The organic solvent is acetonitrile, chloroform, tetrahydrofuran or 1,4- dioxies six One or more in ring；The alkali compounds is one or more in piperidines, pyridine, triethylamine or dimethylamine；Institute State the mixed solvent that eluant, eluent solvent is chloroform, dichloromethane and methyl alcohol, ethanol and acetic acid；Formula（IVa~IVc）Compound and formula （V）The ratio between amount of material of compound and alkaline matter is：1:1.0~3.0:0.1 ~ 0.3, organic solvent volume consumption is with formula （IIIa~IIIc）The amount of the material of compound is calculated as 10 ~ 30 mL/mmol.
The organic solvent is one or more in acetonitrile, chloroform, tetrahydrofuran or Isosorbide-5-Nitrae-dioxane, preferably acetonitrile And tetrahydrofuran（v:v=1:2）；
The alkali compounds is one or more in piperidines, pyridine, triethylamine or dimethylamine, preferably piperidines；
The described reaction time is 1 ~ 10 h, preferably 2 ~ 3 h；
The eluant, eluent solvent is the mixed solvent of chloroform, dichloromethane and methyl alcohol, ethanol and acetic acid, preferably dichloromethane The mixed solvent of alkane, methyl alcohol and acetic acid（v:v:v=200:4:1）；
The consumption of organic solvent is with formula（IVa~IVc）The amount of the material of compound is calculated as 10 ~ 30 mL/mmol, preferably 20 mL/mmol。
Formula（IVa）Shown compound can be prepared in accordance with the following methods：By POCl3With DMF 0o1h systems are stirred under C Vilsmeier reagents, then by formula（VI）DMF is dissolved in, dropwise in Vilsmeier reagents obtained in instillation previous step, 70oUnder C Stirring 8h.
Formula（IVb~IVc）Shown compound can be prepared in accordance with the following methods：By formula（VII）Compound, 4- formyls Base phenylboric acid (VIII) or（IX）, tetra-triphenylphosphine palladium be dissolved in a certain amount of THF, add a certain amount of sodium carbonate Solution, N2It is heated to reflux preparing under protection.
The above-mentioned preparation method being well known to those skilled in the art.
Described triaryl amine coumarin kind compound is specifically applied as follows as the application of dye sensitizing agent：
Triaryl amine coumarin kind compound is dissolved in CH3CN-DMSO（V:V=24:1）In mixed solvent, bilayer TiO is soaked2 The h of film of nanoparticles optoelectronic pole 24.The TiO of the tri-arylamine group compound containing cumarin is loaded2Electrode and platinum to electrode assembling into Sandwich structure, and electrolyte is instilled at edge, introduce inside battery using capillary percolation principle.In 100 mW/cm2Light intensity Under irradiation, photovoltage-current characteristic curve is determined.Its result shows the opto-electronic conversion effect of such triaryl amine coumarin kind compound Rate is 3.36-6.24%.
Triaryl amine coumarin kind compound beneficial effect prepared by the present invention is mainly reflected in：There is provided a kind of three new virtues Amine coumarin kind compound, the compound has preferable light as the DSSC that dye sensitizing agent is assembled into Photoelectric transformation efficiency, be dye sensitizing agent screening add it is new can applied material.
Specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in This：
Embodiment 1
The synthesis of compound IVa
By POCl3 (5.5 mL) is with DMF (10 mL) 0o1h is stirred under C and is obtained Vilsmeier reagents, then by chemical combination Thing V (2.95 g, 7.5 mmol) is dissolved in DMF (10 mL), in dropwise instilling Vilsmeier reagents obtained above, 70oC 8 h of lower stirring, are subsequently added water (100 mL), stir 1 h.CH2Cl2(3 × 80 mL) is extracted, washing, anhydrous sodium sulfate Dry.After being spin-dried for solvent, post separation (CH2Cl2:PE = 9:1) yellow solid (2.1 g, the % of yield 67) is obtained.m.p.: 207- 211 ºC; 1H NMR (400 MHz, CDCl3, δ): 9.92 (s, 1H, CHO), 8.05 (s, 1H, Ar-H), 7.82 (d, J = 4.0 Hz, 1H, Ar-H), 7.76 (d, J = 4.1 Hz, 1H, Ar-H), 7.41-7.36 (m, 5H, Ar-H), 7.25-7.19 (m, 6H, Ar-H), 6.92 (dd, J = 8.7, 2.2 Hz, 1H, Ar-H), 6.83 (d, J = 2.2 Hz, 1H, Ar-H); HREIMS m/z 424.1003 [M+H]+, cacld C26H17NO3S for: 423.0929
The synthesis of compound I
Compound IVa (0.987 g, 2.3 mmol) and cyanoacetic acid V (0.978 g, 11.5 mmol) are dissolved in In THF (20 mL), piperidines (20 mg, 0.23 mmol), N are added2After 12 h of the lower backflow of protection, solvent is spin-dried for, post separation (VHAc: VMeOH: VCH2Cl2=2:8:400) violet solid (971 mg, the % of yield 85) is obtained.m.p.: 284-289 ºC;1H NMR (500 MHz, DMSO, δ): 8.76 (s, 1H, CH=CCN), 8.44 (s, 1H, Ar-H), 7.99 (d, J = 4.3 Hz, 1H, Ar-H), 7.94 (d, J = 4.2 Hz, 1H, Ar-H), 7.64 (d, J = 8.9 Hz, 1H, Ar-H), 7.47 (t, J=7.8 Hz, 4H, Ar-H), 7.31-7.26 (m, 6H, Ar-H), 6.82 (dd, J = 8.8, 2.2 Hz, 1H, Ar-H), 6.59 (d, J = 2.2 Hz, 1H, Ar-H); HREIMS m/z 491.1166 [M+H]+, cacld C29H18N2O4S for: 490.0987
Embodiment 2
The synthesis of compound IVb
Compound VII (1.65 g, 3.5 mmol), 5- aldehyde radical -2- thienyl boric acids VIII (0.65 g, 4.2 Mmol), Pd (PPh3)4(0.40 g, 0.35 mmol) and saturation K2CO3(2 M, 7 mL) are dissolved in THF (18 mL), N218 h of the lower backflow of protection.Reaction solution is extracted three times with dichloromethane, and washing, anhydrous sodium sulfate drying is spin-dried for solvent, post separation (VCH2Cl2: VPE=2:1) red solid (350 mg, the % of yield 20) is obtained.m.p.: 250-252oC; 1H NMR (500 MHz, CDCl3) δ: 9.86 (s, 1H, -CHO), 7.96 (s, 1H, Ar-H), 7.68 (d, J = 4.0 Hz, 1H, Ar-H), 7.62 (d, J = 4.0 Hz, 1H, Ar-H), 7.39-7.37 (m, 1H, Ar-H), 7.37-7.34 (m, 4H, Ar-H), 7.33 (d, J = 8.7 Hz, 1H, Ar-H), 7.31 (d, J = 3.9 Hz, 1H, Ar-H), 7.22-7.18 (m, 6H, Ar-H), 6.92 (dd, J = 8.7, 2.3 Hz, 1H, Ar-H), 6.85 (d, J = 2.2 Hz, 1H, Ar-H); HREIMS m/z 506.0906 [M+H]+, cacld C30H19NO3S2 for: 505.0806.
The synthesis of compound II
Compound IVb (633 mg, 1.25 mmol) and cyanoacetic acid V (134 mg, 1.58 mmol) are dissolved in In THF (20 mL), piperidines (11 mg, 0. 13mmol), N are added2After 12 h of the lower backflow of protection, solvent is spin-dried for, post separation (VHAc: VMeOH: VCH2Cl2=2:8:400) atropurpureus solid (971 mg, the % of yield 41) is obtained.m.p.: 247-249 ºC;1H NMR (500 MHz, DMSO, δ): 8.65 (s, 1H, CH=CCN), 8.48 (s, 1H, coumarin-H), 7.98 (d, J = 4.1 Hz, 1H, Ar-H), 7.84 (d, J = 4.1 Hz, 1H, Ar-H), 7.67 (d, J = 4.0 Hz, 1H, Ar-H), 7.62 (d, J = 3.9 Hz, 1H, Ar-H), 7.60 (d, J = 8.8 Hz, 1H, Ar-H), 7.48-7.41 (m, 4H, Ar-H), 7.30-7.20 (m, 6H, Ar-H), 6.82 (dd, J = 8.7, 2.2 Hz, 1H, Ar-H), 6.60 (d, J = 2.2 Hz, 1H, Ar-H). HREIMS m/z 573.0916 [M+H]+, calcd for C33H20N2O4S2: 572. 0864.
Embodiment 3
The synthesis of compound IVc
Compound VII (209.5 mg, 0.44 mmol), to aldehyde radical phenyl boric acid IX (76.6 mg, 0.51 mmol), Pd(PPh3)4(50.8 mg, 0.04 mmol) and saturation K2CO3(2 M, 1 mL) is dissolved in THF (2 mL), N2Protection 8 h of lower backflow.Reaction solution is extracted three times with dichloromethane, and washing, anhydrous sodium sulfate drying is spin-dried for solvent, post separation (VCH2Cl2: VPE=2:1) Chinese red solid (176 mg, the % of yield 80) is obtained.m.p.: 275-277oC; 1H NMR (500 MHz, CDCl3) δ: 10.02 (s, 1H, -CHO), 7.98 (s, 1H, Ar-H), 7.91(d, J = 8.3 Hz, 2H, Ar-H), 7.83 (d, J = 8.3 Hz, 2H, Ar-H), 7.72 (d, J = 4.0 Hz, 1H, Ar-H), 7.48 (d, J = 4.0 Hz, 1H, Ar-H), 7.40-7.33 (m, 5H, Ar-H), 7.25-7.18 (m, 6H, Ar-H), 6.93 (dd, J = 8.6, 2.2 Hz, 1H, Ar-H), 6.86 (d, J = 2.2 Hz, 1H, Ar-H); HREIMS m/z 500.1329 [M+H]+, cacld C32H21NO3S for: 499.1242.
The synthesis of compound III
Compound IVc (587 mg, 1.17 mmol) and cyanoacetic acid V (534 mg, 6.27 mmol) are dissolved in In THF (20 mL), piperidines (10 mg, 0.12 mmol), N are added2After 12 h of the lower backflow of protection, solvent is spin-dried for, post separation (VHAc: VMeOH: VCH2Cl2=2:8:400) aubergine solid (524 mg, the % of yield 79) is obtained.m.p.: 261-265 ºC;1H NMR (500 MHz, DMSO, δ): 8.60 (s, 1H, CH=CCN), 8.32 (s, 1H, Ar-H), 8.10 (d, J = 8.6 Hz, 2H, Ar-H), 7.92 (d, J = 8.5 Hz, 2H, Ar-H), 7.87 (d, J = 4.0 Hz, 1H, Ar-H), 7.81 (d, J = 4.1 Hz, 1H, Ar-H), 7.62 (d, J = 8.8 Hz, 1H, Ar-H), 7.48- 7.43 (m, 4H, Ar-H), 7.29-7.23 (m, 6H, Ar-H), 6.84 (dd, J = 8.7, 2.3 Hz, 1H, Ar-H), 6.62 (d, J = 2.2 Hz, 1H, Ar-H). HREIMS m/z 567.1398 [M+H]+, calcd for C35H22N2O4S: 566. 1300.
Embodiment 4
Triaryl amine coumarin kind compound as dye sensitizing agent application
The double-deck TiO prepared using silk-screen printing2Film of nanoparticles is used as optoelectronic pole：First on electro-conductive glass FTO One layer of TiO of 20 nm of 12 μm of thickness of print2Particle, 30 min of calcining in Muffle furnace under 450 oC.Before material is contaminated Burned film is immersed into 0.04 molL-1 TiCl4The oC of the aqueous solution 70 pre-processes 30 min, and water is then used respectively And alcohol flushing, hair dryer drying.After calcining 30 min again under the oC of Muffle furnace 450, immersed after being cooled to 80 oC 3×10-4 mol·L-1The acetonitrile of dyestuff is sensitized with the h of DMSO solution room temperature 24.Preparation to electrode：Using silk-screen printing Method, by certain density H2PtCl6Solution is printed on FTO electro-conductive glass, and then 400 oC Muffle furnaces sinter 20 min. Adsorb the TiO of dyestuff2Electrode and platinum instill electrolyte to electrode assembling into sandwich structure at edge（Containing 0.07 mM/L I-）, inside battery is introduced using capillary percolation principle.In 100 mW/cm2Under light intense irradiation, photovoltage-current characteristics is determined Curve.Its result is as shown in table 1：
The DSSC performance parameters that the assembling of the triaryl amine cumarin of table 1 is obtained
Com.p.d Jsc (mA·cm-2) Voc (mV) ff η %
I 9.52 0.54 0.65 3.36
II 12.91 0.59 0.61 4.59
III 14.33 0.69 0.63 6.24

Claims (3)

1. triaryl amine coumarin kind compound of a kind of structure as shown in Formula II and formula III,
。
2. the method for preparing the coumarin kind compound described in claim 1, it comprises the following steps：By formula IV b ~ IVc chemical combination Thing mixes with Formula V with organic solvent, in the presence of alkali compounds, is heated to reflux the h of stirring reaction 1 ~ 10, after reaction completely, Solvent is spin-dried for, residue carries out silica gel column chromatography, the triaryl amine Coumarins shown in acquisition Formula II and formula III with eluant, eluent solvent Compound；
The alkali compounds is one or more in piperidines, pyridine, triethylamine or dimethylamine；The organic solvent is second One or more in nitrile, chloroform, tetrahydrofuran or 1,4- dioxane；
The eluant, eluent solvent is the mixed solvent of chloroform, dichloromethane and methyl alcohol, ethanol and acetic acid；
The ratio between formula IV b ~ IVc compounds and amount of material of Formula V compound and alkaline matter are：1:1.0~3.0:0.1 ~ 0.3, Organic solvent volume consumption is calculated as 10 ~ 30 mL/mmol with the amount of the material of formula IV b ~ IVc compounds,
。
3. a kind of triaryl amine coumarin kind compound as claimed in claim 1 application on the solar cell.
CN201410496693.8A 2014-09-25 2014-09-25 A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin Active CN104311543B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410496693.8A CN104311543B (en) 2014-09-25 2014-09-25 A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410496693.8A CN104311543B (en) 2014-09-25 2014-09-25 A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin

Publications (2)

Publication Number Publication Date
CN104311543A CN104311543A (en) 2015-01-28
CN104311543B true CN104311543B (en) 2017-07-07

Family

ID=52366884

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410496693.8A Active CN104311543B (en) 2014-09-25 2014-09-25 A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin

Country Status (1)

Country Link
CN (1) CN104311543B (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104610251B (en) * 2015-01-29 2017-08-18 浙江工业大学 A kind of coumarin kind compound and its preparation method and application
KR102545509B1 (en) * 2016-06-02 2023-06-21 삼성디스플레이 주식회사 Polycyclic compound and organic electroluminescence device including the same
CN107275362B (en) * 2016-12-28 2020-10-09 上海天马有机发光显示技术有限公司 OLED display panel and contain its electronic equipment
CN109438440B (en) * 2018-11-08 2020-12-01 浙江工业大学 Triarylamine compound containing pyridoquinazolinone and preparation method and application thereof

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4599844B2 (en) * 2004-01-20 2010-12-15 コニカミノルタホールディングス株式会社 Semiconductor for photoelectric conversion material, photoelectric conversion element and solar cell
TWI386400B (en) * 2008-09-25 2013-02-21 Academia Sinica Organic dye - sensitized molecular compounds and their applications
CN101407639B (en) * 2008-11-24 2012-07-04 中国科学院长春应用化学研究所 Organic dye with five-element heterocycle and derivative thereof as conjugate unit, and dye sensitization solar cell prepared thereby
CN101497746B (en) * 2009-03-05 2013-09-04 中国科学院长春应用化学研究所 Organic dye containing thiophen ethylene and dye sensitization solar cell prepared thereby
CN101864187B (en) * 2010-06-11 2013-04-10 北京大学 Dye with low energy level difference, intermediate and preparation method and application thereof
CN103087051A (en) * 2013-01-17 2013-05-08 浙江工业大学 Synthesis and application of coumarin type dye sensitizer
CN103709129A (en) * 2013-12-11 2014-04-09 浙江工业大学 Synthesis and application of diethylamino coumarin dye sensitizer

Also Published As

Publication number Publication date
CN104311543A (en) 2015-01-28

Similar Documents

Publication Publication Date Title
TWI382063B (en) Photosensitive pigments
CN104311543B (en) A kind of synthesis and application of the tri-arylamine group dye sensitizing agent containing cumarin
Cai et al. Molecular engineering of the fused azacycle donors in the DA-π-A metal-free organic dyes for efficient dye-sensitized solar cells
KR20140025456A (en) Materials for electronic devices
CN107253946A (en) Synthesis and application of benzocarbazole dye sensitizer
CN106674204B (en) The carbazole compound of the azophenlyene containing dibenzo, preparation method and applications
Maglione et al. Novel pyran based dyes for application in dye sensitized solar cells
Chiu et al. A new series of azobenzene-bridged metal-free organic dyes and application on DSSC
CN103936729B (en) The synthesis of a kind of N-butyl carbazoles dye sensitizing agent and application
CN103709129A (en) Synthesis and application of diethylamino coumarin dye sensitizer
Arrechea et al. Charge recombination losses in thiophene-substituted porphyrin dye-sensitized solar cells
Matsui et al. Long-term stability of novel double rhodanine indoline dyes having one and two anchor carboxyl group (s) in dye-sensitized solar cells
Jia et al. New D–π–A dyes incorporating dithieno [3, 2-b: 2′, 3′-d] pyrrole (DTP)-based π-spacers for efficient dye-sensitized solar cells
KR20090086032A (en) Dyes for dye-sensitized solar cells and solar cells comprising the same
CN104311549B (en) A kind of synthesis and application of carbazoles dye sensitizing agent
CN104610251B (en) A kind of coumarin kind compound and its preparation method and application
CN106831748B (en) Tri-arylamine group compound and preparation method thereof is preparing the application on solar battery
Guo et al. Structure-property relationship of different electron donors: new organic sensitizers based on bithiazole moiety for high efficiency dye-sensitized solar cells
Mane et al. DA-π-A organic dyes for dye-sensitized solar cells: Effect of π-bridge length between two acceptors on photovoltaic properties
CN108586315A (en) A kind of benzo carbazole class compound and the preparation method and application thereof
Zani et al. An unusual thiazolo [5, 4-d] thiazole sensitizer for dye-sensitized solar cells
KR20160003566A (en) Photosensitive porphyrin-based dye and dye-sensitized solar cell
CN101979390A (en) Bithiazole derivates and use thereof
CN108690366B (en) Novel N, N-diethylaniline solar dye sensitizer and preparation and application thereof
Han et al. New difluorenylaminocoumarin photosensitizers for dye-sensitized solar cells

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant