CN107163035B - A kind of oligo-thiophenes organic micromolecule and its preparation method and application - Google Patents
A kind of oligo-thiophenes organic micromolecule and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of oligo-thiophenes organic micromolecules and its preparation method and application；The small organic molecule is the oligo-thiophenes organic micromolecule compound containing oxadiazoles, it is with preferable thermal stability and good dissolubility, and there is wider absorption spectrum in ultraviolet-visible light area, organic molecule solar cell is applied to as photovoltaic material, show preferable photoelectric converting function, and it also has preferable antibacterial action, can be used as the use of the antimicrobial DP finish such as gram-positive bacterium and gramnegative bacterium.
Description
Technical field
The present invention relates to a kind of small organic molecule photovoltaic material and its preparation method and application, in particular to a kind of oligomerization thiophene
Pheno organic micromolecule and preparation method thereof and in organic molecule solar cell application or in antibacterial medicines
Using belonging to organic photoelectrical material field and biomedicine field.
Background technique
The world today, along with the rapid progress of human civilization and society, economic fast development, need of the mankind to the energy
The amount of asking is more and more.But people result in energy crisis to the excessive use of the fossil fuel as conventional energy resource, this makes
People begin look for and tap a new source of energy.Solar energy is more and more paid attention to as the renewable energy of clean and environmental protection, will
The solar battery that solar energy is converted into electric energy becomes the hot spot of scientist's research.Organic photovoltaic material holds with materials synthesis
Easily, light weight, can the advantages that wide range operation, at low cost, flexibility be good and large-scale application, attract wide attention.It is organic
The main organic small molecule material of photovoltaic material and polymer material.There are purification difficults, device efficiency repeatability for polymer material
The some shortcomings such as difference, this limits the application of polymer to a certain extent.However, organic small molecule material has structure bright
Really, it is easy to the advantages that purifying and is reproducible, therefore the research of small organic molecule photovoltaic material becomes the research of solar battery
Hot spot.
In recent years, the development of small organic molecule photovoltaic material and application were very fast.2010, Tyler seminar report
Pechmann small organic molecule photovoltaic material, energy conversion efficiency is less than 2%.2012, Heeger seminar reported
Organic small molecule material p-DTS (PTTh2)2Incident photon-to-electron conversion efficiency reaches 6.7%.2014, Yin seminar reported based on three
Four kinds of small organic molecule photovoltaic materials of aniline and DPP, maximum conversion 4%.With the continuous development of science and technology, have
The application of machine small molecule in solar cells is constantly brought forth new ideas, and the organic molecule solar cell highest of latest report converts effect
Rate reaches 12.50%, can almost compare favourably with the application of polymer material in solar cells.But in the prior art may be used
Using the organic compound limited amount as organic molecule solar cell photovoltaic material, it is difficult to meet existing demand.
Summary of the invention
In view of the defects existing in the prior art, that the purpose of the invention is to provide a kind of dissolubilities is good, thermal stability is good
And the oligo-thiophenes organic micromolecule compound with the novel modification containing oxadiazoles compared with wide absorption spectrum.
Another object of the present invention is to be that provide the oligo-thiophenes organic micromolecule is having as photovoltaic material
Application in machine small molecule solar battery, shows preferable photovoltaic performance, and single layer photoelectric conversion efficiency is more than 1%.
Third object of the present invention is to provide the oligo-thiophenes organic micromolecule as on antibacterial medicines
Using especially there is good inhibiting effect to the growth of gram-positive bacterium and gramnegative bacterium.
Fourth object of the present invention be to provide a kind of easy to operate, reaction condition it is mild prepare the oligomerization thiophene
The method of pheno organic micromolecule.
In order to achieve the above technical purposes, the present invention provides a kind of oligo-thiophenes organic micromolecules, with 1 knot of formula
Structure:
R and R1 independent choice C1~C10Alkyl.
Preferred scheme, R C4~C8Alkyl；More preferably C6H13。
Preferred scheme, R1For C5~C9Alkyl, more preferably C8H17。
The present invention also provides the applications of the oligo-thiophenes organic micromolecule described in one kind, answer as photovoltaic material
For organic molecule solar cell.
Preferred scheme, the oligo-thiophenes organic micromolecule are applied to preparation organic molecule solar cell device
Part.
More preferably scheme, after the oligo-thiophenes organic micromolecule is mixed with electron-acceptor material, using solvent
Dissolution, gained mixture is coated on electro-conductive glass and film is made, then prepares metal electrode on film to get small organic molecule
Solar cell device.
Preferred scheme, the electron-acceptor material are PC61BM、PC71BM、PC61BM derivative, PC71BM derivative,
At least one of organic matter electron acceptor.
Preferred scheme, the solvent are at least one of methylene chloride, tetrahydrofuran, chloroform.
Organic molecule solar cell of the invention, using oligo-thiophenes organic micromolecule as donating substances, with
PC61The receptive materials such as BM, using acetylacetone,2,4-pentanedione zirconium (ZrAcac), poly- 3,4-ethylene dioxythiophene (PEDOT) and poly- to styrene
Azochlorosulfonate acid anion (PSS) is used as decorative layer, and 0.5% 1,8- diiodo-octane (DIO) is used as additive, photoelectric conversion effect
Rate is more than 1%.
The preparation process of present invention preparation small organic molecule solar cell device are as follows: by DHOT and electron-acceptor material
(PC61BM、PC71BM it) mixes, solvent and additive is added, dissolve mixture, it is thin coated in being prepared on electro-conductive glass
Film, spin coating ZrAcac or PEDOT:PSS solution are made into the small organic molecule sun as decorative layer, evaporation metal electrode on film
It can battery device.
The present invention also provides the applications of the oligo-thiophenes organic micromolecule, by oligo-thiophenes organic micromolecule
As Antibiotics usage.
Preferred scheme, the oligo-thiophenes organic micromolecule is as thin to gram-positive bacterium and Gram-negative
The growth of bacterium has the medicinal application of inhibiting effect.
The present invention also provides a kind of preparation methods of oligo-thiophenes organic micromolecule, method includes the following steps:
1) -2 formylhydrazine of 5- bromothiophene and carbon disulfide obtain 2 intermediate of formula by ring-closure reaction；
2) 2 intermediate of formula uses in potassium hydroxide and after salinization, then carries out N- alkylated reaction with alkane iodide, obtains formula
3 intermediates；
3) substitution reaction occurs for 3 intermediate of formula and tributyl (4- alkyl-2-thienyl) stannane, obtains 4 intermediate of formula；
4) 4 intermediate of formula obtains 5 intermediate of formula by NBS bromination；
5) 5 intermediate of formula and 2, bis- (trimethyl-tin-radical) thiophene of 5- carry out disubstituted reaction to get；
R and R1Independent choice C1~C10Alkyl.
Preferred scheme, 1) in, carbon disulfide is slowly added into alkali/mixed alkoxide solution of -2 formylhydrazine of bromothiophene containing 5-
Reflux, obtains 2 intermediate of formula.
Preferred scheme, 2) in, 2 intermediate of formula and KOH obtain nitrogen in room temperature reaction in MeOH/THF in the mixed solvent
Potassium salt compound；The nitrogen potassium salt compound and iodohexane, in room temperature reaction, obtain 3 intermediate of formula in DMF solvent.
Preferred scheme, 3) in, 3 intermediate of formula and tributyl (4- alkyl-2-thienyl) stannane in toluene solvant,
Under tetrakis triphenylphosphine palladium catalytic action, is reacted in 110~120 DEG C, obtain 4 intermediate of formula.
Preferred scheme, 4) in, it is molten in chloroform/acetic acid mixing of 4 intermediate containing formula under the conditions of at 0 DEG C or less and being protected from light
In liquid, NBS is added, then be warmed to room temperature reaction, obtains being 5 intermediates.
Preferred scheme, 5) in, 5 intermediate of formula and 2, bis- (trimethyl-tin-radical) thiophene of 5- are in toluene solvant, four (three
Phenylphosphine) palladium chtalyst effect under, in 110~120 DEG C reaction to get.
Compared with the prior art, technical solution of the present invention bring advantageous effects:
Oligo-thiophenes class conjugation small organic molecule of the invention includes a large amount of polarity thia ring and oxaza etc., simultaneously
A large amount of alkyl branches are introduced, is conducive to the solubility property for improving oligo-thiophenes class conjugation small organic molecule, dissolves in dichloro
The Conventional solvents such as methane, furans improve its processing performance, while also effectively improving its short circuit current (Jsc) value.
Include sulphur, oxygen, nitrogen isopolarity atom in oligo-thiophenes organic micromolecule of the invention, there is stronger electrophilic
Ability reduces HOMO energy level, to improve open-circuit voltage (Voc) value, and guarantee its good air stability.
Oligo-thiophenes organic micromolecule of the invention contains larger planar conjugate system, and intermolecular force is strong, has
Ultraviolet and near-infrared is infrared visible light-responded, has preferable absorption to the sunlight of 350~550nm range, ABSORPTION EDGE has
Red shift, and there is apparent acromion to occur at 425nm.
The organic photovoltaic devices of oligo-thiophenes organic micromolecule preparation of the invention have good photovoltaic performance, list
Layer device photoelectric conversion efficiency is 1% or more.
Oligo-thiophenes organic micromolecule structure of the invention is simple, and molecular weight is small, convenient for purification, multi-stage synthesis reproducibility
It is good.
Oligo-thiophenes organic micromolecule of the invention has excellent thermal stability, solubility property, film forming and film
Form stable.
Oligo-thiophenes organic micromolecule of the invention includes oxadiazoles modification group, blue to gram-positive bacterium and leather
The growth of family name's negative bacteria has obvious inhibiting effect, can be using preparation antibacterials.
Detailed description of the invention
[Fig. 1] is the TGA curve of DHOT small organic molecule prepared by the embodiment of the present invention 1.
[Fig. 2] is the ultraviolet-visible absorption spectroscopy of DHOT small organic molecule prepared by the embodiment of the present invention 1.
[Fig. 3] is the electrochemical analysis of DHOT small organic molecule prepared by the embodiment of the present invention 1.
[Fig. 4] is the hole mobility of DHOT small organic molecule prepared by the embodiment of the present invention 1.
[Fig. 5] is the photoelectric conversion efficiency of DHOT small organic molecule prepared by the embodiment of the present invention 1.
Specific embodiment
Following embodiment is intended to further illustrate the content of present invention, rather than limits the protection model of the claims in the present invention
It encloses.
Reagent and condition:
Main agents are as follows: 5- bromothiophene -2- formic acid, ethyl alcohol, the concentrated sulfuric acid, hydrazine, potassium hydroxide, tetrahydrofuran, toluene, two
Nitric sulfid, chloroform, iodohexane and N- bromo-succinimide, the production of Shanghai Chinese medicines group；Tetrakis triphenylphosphine palladium, tributyl
The production of source company is foreignized in (4- octyl -2- thienyl) stannane and 2, bis- (trimethyl-tin-radical) thiophene of 5-, peace.Toluene is using preceding needing
Dry water removal, other reagents be it is commercially available, analyze it is pure, do not do any processing using preceding.
Other chemical reagent being related in following embodiments unless otherwise specified, commercially obtain；It is related to
The experimental method arrived is unless otherwise specified conventional method.
5- bromothiophene -2- formylhydrazine the raw material of use can directly be bought, and can also simply be synthesized by the following method: with
5- bromothiophene -2- formic acid, with alcohol reflux, obtains 5- bromothiophene -2- Ethyl formate, 5- bromothiophene -2- first under sulfuric acid catalysis
Acetoacetic ester and hydrazine flow back in ethanol solution, obtain -2 formylhydrazine of 5- bromothiophene.
Embodiment 1
Specific reaction route is as follows:
Steps are as follows:
5- (5- bromothiophene -2- base) -1,3,4- oxadiazoles -2 (3H)-thioketones (4)
5- bromothiophene -2- formylhydrazine (0.8843g, 4.0mmol) is added in round-bottomed flask, potassium hydroxide (0.3366g,
6.0mmol), dehydrated alcohol 35mL, CS2(0.5484mL, 8.0mmol), magnetic agitation reflux, adds carbon disulfide every 2.0h
0.5mL is added 2 times, is stopped after reacting 8.0h.After the reaction was completed, decompression is spin-dried for pumping solvent, and 30mL water is added, acutely shakes,
It filters to get filtrate, adjusts PH to 2-3 or so, a large amount of faint yellow solids are precipitated, filter to obtain faint yellow solid 4 (0.843g, yield
80.1%).
1H NMR result is as follows: δ 7.63 (d, J=4.0Hz, 1H), 7.44 (d, J=4.0Hz, 1H).
- 2 (3H)-thioketones (6) of 5- (5- bromothiophene -2- base) -3- hexyl -1,3,4- oxadiazoles
4 (1.0525g, 4.0mmol), KOH (0.2244g, 4.0mmol), MeOH (25mL), THF are added in round-bottomed flask
(25mL), room temperature magnetic agitation stop after reacting 8.0h.After the reaction was completed, decompression is spin-dried for pumping solvent, and THF10mL is added to continue
It is spin-dried for vacuum drying and obtains intermediate 5.
Above-mentioned nitrogen sylvite is dissolved with DMF 30mL, iodohexane (1.697g, 8.0mmol) is added into reaction flask, room temperature magnetic
Power stirring, reaction stop afterwards for 24 hours.After the reaction was completed, dilute hydrochloric acid (5%, 20mL) is added, methylene chloride 25mL extraction, extraction is added
It takes 3 times, combining extraction liquid, organic phase washs 3 times with saturated salt solution 25mL and removes extra DMF, and anhydrous sodium sulfate is dry, rotation
Dry to remove solvent, pillar layer separation (solvent: methylene chloride: petroleum ether=1:5) obtains white solid 6 (0.733g, yield
52.77%).
1H NMR result is as follows: δ 7.45 (d, J=4.0Hz, 1H), 7.13 (d, J=4.0Hz, 1H), 3.30 (t, J=
7.4Hz,2H),1.90–1.27(m,12H),0.92(t,3H)。
3- hexyl -5- (4 '-octyls-[2,2 '-Dithiophene] -5- base) -1,3,4- oxadiazoles -2 (3H)-thioketones (7)
By compound 6 (1.384g, 4.0mmol), tributyl (4- octyl -2- thienyl) stannane (2.626g,
It 5.4mmol) is dissolved in dry toluene 60mL, leads to argon gas 20min, guarantees reaction system anaerobic.Four (three are added into reaction system
Phenylphosphine) palladium (277mg) be to slowly warm up to 115 DEG C reaction for 24 hours.After reaction, it pours the mixture into water, methylene chloride extraction
It takes.Dichloromethane extract is collected, after revolving removes solvent, crude product petroleum ether: methylene chloride (3:1) makees eluant, eluent and crosses silicon
Rubber column gel column purification.Obtain faint yellow solid 7 (1.04g, yield 56.28%).
1H NMR result is as follows: δ 7.59 (d, J=3.9Hz, 1H), 7.17 (d, J=3.9Hz, 1H), 7.13 (s, 1H),
6.92 (s, 1H), 3.33 (t, J=7.3 2H), 2.61 (t, J=7.7Hz, 2H), 1.90-1.20 (m, 20H), 0.89 (m,
6H)。
- 2 (3H)-thioketones of 5- (5 '-bromo- 4 '-octyl-[2,2 '-Dithiophene] -5- base) -3- hexyl -1,3,4- oxadiazoles
(8)
Reactant 7 (1.315g, 2.85mmol), chloroform 25mL, acetic acid 25mL are sequentially added in reaction flask.It is kept away at 0 DEG C
Under the conditions of light, NBS (0.559g, 3.14mmol) is added portionwise, is then warmed to room temperature reaction overnight.After reaction, decompression rotation
Evaporate excess of solvent, crude product petroleum ether: methylene chloride (4:1) crosses silicagel column and obtains light green solid 8 (0.78g, yield
50.87%).
1H NMR result is as follows: δ 7.58 (d, J=3.9Hz, 1H), 7.12 (d, J=3.9Hz, 1H), 6.99 (s, 1H),
3.33–3.29(m,2H),2.59–2.55(m,2H),1.92–1.22(m,20H),0.95–0.86(m, 6H)。
The synthesis of compound DHOT
By compound 8 (0.416g, 0.859mmol), 2,5- bis- (trimethyl-tin-radical) thiophene (0.101g, 0.246mmol)
It is dissolved in dry toluene 20mL, tetrakis triphenylphosphine palladium (28mg) is added into reaction system under argon gas protective condition, is warming up to
110 DEG C of reaction 36h.After, it pours the mixture into water, methylene chloride extraction crosses silicagel column after being spin-dried for solvent, uses petroleum
Ether: methylene chloride (1:2) makees eluant, eluent, obtains dark red solid DHOT (70mg, yield 28.34%).
1H NMR result is as follows: δ 7.61 (d, J=3.9Hz, 2H), 7.19 (d, J=3.8Hz, 2H), 7.15 (d, J=
2.3Hz, 2H), 3.31 (t, J=7.4Hz, 4H), 2.83 (t, 4H), 1.98-1.18 (m, 40H), 0.92 (m, 12H).
Application example: the Photovoltaic Properties of DHOT
Device architecture is ITO/PEDOT:PSS/DHOT:PC71BM/ZrAcac/Al
Using above-mentioned small organic molecule as working media, the method for preparation small organic molecule solar cell is the present invention: will
DHOT and suitable PC61BM or PC71BM and its derivative or other material mixings that can be used as electron acceptor, are added
Suitable solvent dissolution, prepares one layer of translucent film by conventional spin coating or other modes on ITO electro-conductive glass,
Then by way of vacuum evaporation in small organic molecule evaporation metal electrode, prepare organic molecule solar cell device
Part.The PC of the DHOT and 5mg of 5mg71The dissolution of 0.5mL o-dichlorohenzene is added, by spin coating mode through PEDOT:PSS in BM mixing
The film that one layer of about 100nm thickness is prepared on the electro-conductive glass of modified, as active layer, then by way of vacuum evaporation
Metal electrode is prepared on active layer with aluminium.Its device performance shows themselves in that short-circuit current density is 3.99mA/cm2, open-circuit voltage
For 0.84V, fill factor 30.7%, simulated solar irradiation (A.M.1.5,100mW/cm2) under energy conversion efficiency be
1.03%.
Small organic molecule spectrum property
Conjugation organic small molecule material spectral absorption of the invention is analyzed using uv-visible absorption spectra instrument, thus
Judge that it captures photon ability.Small organic molecule is in the uv-visible absorption spectra of chloroform soln and solid film such as Fig. 2 institute
Show.
Red line indicates that the absorption curve of small organic molecule chloroformic solution, black curve then indicate the absorption of solid film in figure
Curve.Under solution and filminess, DHOT shows wider absorption platform, and absorption region is between 300~600nm.?
Under solution state, the absorption peak of short wave ranges 335nm, key factor is in the π-π * electron transition on main chain；And at 425nm
Absorption maximum is that electric charge transfer (ITC) is formed by the receptor unit on main chain and between donor monomer.Under filminess, small point
The maximum absorption wavelength red shift 10nm of son, and there is apparent absorbing shoulder band, it shows small molecule and has under filminess
There is stronger intermolecular force.Absorption spectrum is consistent with the radiation spectrum of the sun, preferably solves photovoltaic material small molecule
Compound and the unmatched problem of solar radiation spectrum, can be absorbed more solar energy, and be converted into electric energy and provide
Basis is one of the factor for obtaining efficient solar battery key.
Small organic molecule chemical property
We have obtained the initial oxidation reduction potential of small molecule using cyclic voltammetry (CV), and then are calculated corresponding
HOMO and lumo energy.Fig. 3 show the cyclic voltammetry curve figure of DHOT, and electrolyte is 0.1mol/L Bu4NPF6Acetonitrile it is molten
Liquid, sweep speed 50mV/s.From figure 3, it can be seen that DHOT shows quasi- invertibity, Oxidation Doping electricity in anode region
Stream is apparently higher than the n- doping electric current of reduced zone.According to following equation: EHOMO=-e (Eox+4.4)(eV)；ELUMO=-e
(Ered+ 3.59) (eV) obtains the HOMO and lumo energy of small organic molecule.Wherein: EoxFor initial oxidation potential, EredFor starting
Reduction potential.Relative to Ag/AgCl reference electrode, the initial reduction current potential of DHOT is -0.81V, corresponding lumo energy is -
3.59eV.Initial oxidation potential is 1.05V, and corresponding HOMO energy level is -5.45 eV.It can be obtained according to HOMO and lumo energy
Electrochemistry energy gap to DHOT is 1.86eV, and electrochemistry energy gap and optical energy gap are than more consistent.
Small organic molecule hole mobility
Charge mobility is the another important parameter for influencing conjugation small organic molecule performance, because it directly influences charge
Transmission.We determine DHOT donor material and PC under optimal performance using space limitation charge current method (SCLC)71BM is total
The hole mobility of mixed film.Its device architecture is ITO/PEDOT:PSS/DHOT:PC71BM/ZrAcac/Al is based on Poole-
Frenkel law, formula are as follows:
Wherein J indicates current density, unit A/m2；μ0For null field mobility, ε0For dielectric constant under vacuum, εrFor object
Matter relative dielectric constant, d are the thickness of device, V=Vappl-Vbi, wherein VapplFor applied voltage, VbiFor built in field.According to
Above formula and Fig. 4, calculate DHOT 0.5% 1,8- diiodo-octane (DIO) as additive under hole mobility such as table 1
It is shown, it is of substantially equal with electron mobility, it can be used as solar cell photovoltaic material.
Small organic molecule photovoltaic performance (solar cell properties)
Shown in Fig. 5, DHOT and PC is based in the presence of DIO is as additive71In the device that BM is blended, open-circuit voltage is
0.84V, short circuit current 3.99mA/cm2, fill factor 30.70%, and then obtain higher energy conversion efficiency, DHOT
Photovoltaic Device Performance is as shown in table 1.Solar cell transfer efficiency can be improved by optimised devices and using different additive.
The performance of 1 DHOT photovoltaic device of table
The solubility property of small organic molecule
Small organic molecule is in methylene chloride, chloroform, tetrahydrofuran, and dissolution is good in the common solvents such as toluene.
The external resisting gram-positive bacterium of DHOT and the active research of gramnegative bacterium
DHOT of the invention belongs to furodiazole derivative, raw to gram-positive bacterium and gramnegative bacterium
With good inhibiting effect, therefore oxadiazole derivatives of the invention can also be using preparation antibacterials.
The compounds of this invention can be measured as the activity of antibacterial by the biological test of many standards.
Strain is as follows: staphylococcus aureus, bacillus subtilis, Escherichia coli, pseudomonas aeruginosa is by microorganism
Teaching and research room provides.
Using MIC (μ g/mL) value of agar dilution measurement compound, each drug solution concentration is 3 times parallel, and
Microtiter plate bottom marks bacteria name.
The preparation of antibacterials stoste: being configured to 2mg/mL solution after methanol dissolution, with filtration method degerming.
The preparation of drug containing agar stoste: stoste is diluted to multiple concentration gradients with dilution method.1mL is taken to be added to respectively
It has performed in the plate well of internal diameter 90mm of label.It takes in sterilized 50 DEG C of M-H agar 19mL to plate well, mixes again
It is cooling after bacterium.
Inoculation: being inoculated in plate one by one with inoculator, each inoculum concentration be 1~2 μ l (bacteria containing amount is about 5 ×
105CFU/mL).It is inoculated with the growth control plate of not drug containing, finally to check the survival shape for testing strain in whole experiment process
State.
Be incubated for: plate is placed in 37 DEG C and is incubated for for 24 hours.
As a result judge: it is the compound to detection strain that bacterium colony grows the lowest concentration of drug being totally constrained completely
MIC。
DHOT Determination of Antibacterial Activity result is as indicated with 2.
2 DHOT Determination of Antibacterial Activity result of table
The result shows that DHOT compound is to staphylococcus aureus, bacillus subtilis, Escherichia coli, P. aeruginosa
Bacterium has certain inhibiting effect.
The present invention has synthesized the oligo-thiophenes organic micromolecule material containing oxadiazoles for the first time, which has
Higher thermal stability and preferable extinction characteristic and good solution processability, we are used for small organic molecule sun electricity
Chi Shang proves to have preferable light transfer characteristic by tentatively attempting, and this kind of organic small molecule material is used for organic solar
Battery has universality, and the application of only solar cell does not provide new donor material, it may also be used for the preparation of antibacterials.
The present invention is described referring to specific embodiment and embodiment.However the present invention be not limited to it is only described
Embodiment and examples of implementation.It will be appreciated by those of ordinary skill in the art that this patent is based on, without departing from claims
Defined by can carry out many changes and substitution under the scope of the present invention.
Claims (10)
1. a kind of oligo-thiophenes organic micromolecule, it is characterised in that: have 1 structure of formula:
R and R1Independent choice C1~C10Alkyl.
2. oligo-thiophenes organic micromolecule according to claim 1, it is characterised in that:
R is C4~C8Alkyl；
R1For C5~C9Alkyl.
3. oligo-thiophenes organic micromolecule according to claim 2, it is characterised in that:
R is C6H13, R1For C8H17。
4. the application of the described in any item oligo-thiophenes organic micromolecules of claims 1 to 3, it is characterised in that: as photovoltaic
Material is applied to organic molecule solar cell.
5. the application of oligo-thiophenes organic micromolecule according to claim 4, it is characterised in that: the oligo-thiophenes class
Small organic molecule is applied to preparation small organic molecule solar cell device.
6. the application of oligo-thiophenes organic micromolecule according to claim 5, it is characterised in that: by the oligo-thiophenes
It after organic micromolecule is mixed with electron-acceptor material, is dissolved using solvent, gained mixture is coated on electro-conductive glass and is made
Film, then metal electrode is prepared on film to get organic molecule solar cell device.
7. the application of the described in any item oligo-thiophenes organic micromolecules of claims 1 to 3, it is characterised in that: be applied to system
Standby antibacterials.
8. the application of oligo-thiophenes organic micromolecule according to claim 7, it is characterised in that: the oligo-thiophenes class
Small organic molecule is applied to the drug that preparation has inhibiting effect to the growth of gram-positive bacterium and gramnegative bacterium.
9. the preparation method of oligo-thiophenes organic micromolecule described in claim 1, it is characterised in that: the following steps are included:
1) 5- bromothiophene -2- formylhydrazine and carbon disulfide obtain 2 intermediate of formula by ring-closure reaction；
2) 2 intermediate of formula uses in potassium hydroxide and after salinization, then carries out N- alkylated reaction with alkane iodide, obtains in formula 3
Mesosome；
3) substitution reaction occurs for 3 intermediate of formula and tributyl (4- alkyl-2-thienyl) stannane, obtains 4 intermediate of formula；
4) 4 intermediate of formula obtains 5 intermediate of formula by NBS bromination；
5) 5 intermediate of formula and 2, bis- (trimethyl-tin-radical) thiophene of 5- carry out disubstituted reaction to get；
R and R1Independent choice C1~C10Alkyl.
10. the preparation method of oligo-thiophenes organic micromolecule according to claim 9, it is characterised in that:
1) in, carbon disulfide is slowly added into the alkali/mixed alkoxide solution of -2- formylhydrazine of bromothiophene containing 5- and flows back, and obtains in formula 2
Mesosome；
2) in, 2 intermediate of formula and KOH obtain nitrogen potassium salt compound in room temperature reaction in MeOH/THF in the mixed solvent；It is described
Nitrogen potassium salt compound and iodohexane, in room temperature reaction, obtain 3 intermediate of formula in DMF solvent；
3) in, stannane is in toluene solvant for 3 intermediate of formula and tributyl (4- alkyl-2-thienyl), in tetrakis triphenylphosphine palladium
Under catalytic action, is reacted in 110~120 DEG C, obtain 4 intermediate of formula；
4) in, under the conditions of at 0 DEG C or less and being protected from light, in chloroform/acetic acid mixed solution of 4 intermediate containing formula, NBS is added, then
It is warmed to room temperature reaction, obtains 5 intermediate of formula；
5) in, 5 intermediate of formula and 2, bis- (trimethyl-tin-radical) thiophene of 5- are catalyzed in tetrakis triphenylphosphine palladium and make in toluene solvant
Under, in 110~120 DEG C reaction to get.
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| CN101402629A (en) * | 2008-11-19 | 2009-04-08 | 云南大学 | Synthesis and uses of terthienyl and derivatives thereof |
| CN102936245A (en) * | 2011-08-15 | 2013-02-20 | 南开大学 | Preparation for photoelectric material |
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| CN102936245A (en) * | 2011-08-15 | 2013-02-20 | 南开大学 | Preparation for photoelectric material |
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