CN105061730B - Fluorine-containing phenanthrene is for quinoxaline and the conjugated polymer of thiophene - Google Patents
Fluorine-containing phenanthrene is for quinoxaline and the conjugated polymer of thiophene Download PDFInfo
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- CN105061730B CN105061730B CN201510449945.6A CN201510449945A CN105061730B CN 105061730 B CN105061730 B CN 105061730B CN 201510449945 A CN201510449945 A CN 201510449945A CN 105061730 B CN105061730 B CN 105061730B
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- quinoxaline
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- 0 C*(C)c1ccc(-c2cc(F)c(*(C)C)c3c2nc(c2ccc(*)cc2c2c4ccc(O)c2)c4n3)[s]1 Chemical compound C*(C)c1ccc(-c2cc(F)c(*(C)C)c3c2nc(c2ccc(*)cc2c2c4ccc(O)c2)c4n3)[s]1 0.000 description 6
- WFPUDDCTYPEYGQ-UHFFFAOYSA-N Cc1cccc(C(C(c2cccc(O)c2)=O)=O)c1 Chemical compound Cc1cccc(C(C(c2cccc(O)c2)=O)=O)c1 WFPUDDCTYPEYGQ-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a kind of fluorine-containing luxuriant and rich with fragrance for quinoxaline and the conjugated polymer of thiophene, while the energy gap and HOMO energy levels of polymer are reduced, the need for meeting polymer photovoltaic cell photoactive layer electron donor material.General structure of the present invention is as follows：Polymer disclosed by the invention has HOMO energy levels more deeper than polymer D, can be deep to 5.67eV, can be obtained applied in photovoltaic cell>0.89V high open circuit voltage.
Description
Technical field
The invention belongs to filed of functional, and in particular to a kind of fluorine-containing phenanthrene is for quinoxaline and the conjugated polymers of thiophene
Thing.
Background technology
Polymer photovoltaic cell is a kind of photovoltaic device converted solar energy into electrical energy, due to low cost, is manufactured
Journey is simple and light weight is easy to carry etc., and outstanding advantages are favored by scientific research personnel.How the photoelectric transformation efficiency of battery is improved
Make it possible to commercially produce be the field be currently badly in need of solve key technical problem.The work being made up of donor and acceptor material
Property layer be device core, in view of in the case of electing fullerene derivate (PCBM) as current acceptor material, therefore opening more
Send out high-efficiency polymer donor material most important to improving cell photoelectric conversion efficiency.
Polymer as device photoactive layer chief component, its absorption spectrum influence battery short circuit current flow, most
The difference of lowest unoccupied molecular orbital (LUMO) energy level of high occupied orbital (HOMO) energy level and PCBM determines the open-circuit voltage of device.Therefore,
Preferable polymeric material should have wider absorption to contain narrower optical energy gap, be conducive to the short circuit electricity of boost device
Stream；There is relatively low HOMO energy levels simultaneously, it is ensured that device results in larger open-circuit voltage.One kind will to electric unit (D) with
Short of electricity unit (A) is alternatively formed D-A type conjugated polymer backbone, realized by intermolecular interaction to material energy level and
The method of energy gap regulation turns into the important channel for developing efficient donor polymer at present.
Quinoxaline molecule draws electrically stronger nitrogen-atoms because itself having two, is used as the new short of electricity unit application of a class
Good result is obtained in polymer and in the devices, the concern of scientific research personnel is enjoyed in recent years.Such as material FTQ
(Journal of Materials Chemistry C.2013,1,630-637), the polymer is by quinoxaline and thiophene copolymerization
Form.Its absorption bands is located at 300-730nm, and to absorb the strongest at 360nm and 622nm, ABSORPTION EDGE is 730nm, correspondence
Optical energy gap is 1.70eV；Oxidizing potential is 0.79V, and correspondence HOMO energy levels are -5.51eV.The material is blended what is prepared with PCBM
Polymer battery best photoelectric conversion efficiency is 5.27%, and wherein open-circuit voltage is 0.87V, and short circuit current flow is 10.11mA/cm2。
Although above-mentioned material has been achieved for good opto-electronic conversion result, in being due to such polymer molecular structure
Contained quinoxaline unit, its 2,3 are substituted by phenyl, and resulting steric hindrance, which is acted on, causes two phenyl ring and quinoxaline point
Sub- backbone structure forms certain torsion, it is impossible to which coexist same plane, cause polymer molecule conjugated degree reduction, optical energy gap compared with
Sunshine can not be effectively absorbed greatly, produces and carries out opto-electronic conversion compared with multi-photon, and performance is the short circuit current flow of battery in the devices
It is less than normal, as the important bottleneck for hindering the lifting of device photoelectric conversion efficiency.
The content of the invention
In view of the shortcomings of the prior art, present invention exploitation is a kind of is given based on the fluorine-containing luxuriant and rich with fragrance D-A type for quinoxaline-thiophene-structure
Body polymeric material, material property is optimized by improving the molecular structure of modified polymer, final to realize lifting photovoltaic device light
The purpose of photoelectric transformation efficiency.
To achieve these goals, the technical solution adopted by the present invention is as follows：Quinoline is substituted using phenanthrenequione structural compounds
Containing 5 aromatic rings in the substituent phenyl ring that quinoline unit is 2,3, the polymer molecule skeleton that program design is obtained, so that group
Into a complete coplanar structure, there is higher conjugated degree compared with the molecule that phenyl replaces, can further widen
The absorption spectrum of polymer produces narrower optical energy gap, and the short circuit current flow of effective boost device is capable of in performance in the devices.This
Outside, it is same in polymer backbone conformation to retain the fluorine atom for drawing electronic capability stronger, to reduce the HOMO energy levels of polymer, protect
Demonstrate,proving device has higher open-circuit voltage.
Specifically, a kind of fluorine-containing phenanthrene of the present invention is for quinoxaline and the conjugated polymer of thiophene, its general structure
As shown in formula I：
In formula, R1、R2Can with identical also different,
Work as R1During=H, R2It is the alkyl or alkoxy for the straight or branched that carbon number is 4 to 20.
Work as R2During=H, R1It is the alkyl or alkoxy for the straight or branched that carbon number is 4 to 20.
Work as R1=R2When, it is the alkyl or alkoxy of 4 to 20 straight or branched.
The present invention has following technical characterstic：
Work as R2During for hydrogen atom, the described fluorine-containing luxuriant and rich with fragrance structure such as institute of formula II for quinoxaline and the conjugated polymer of thiophene
Show：
Work as R1During for hydrogen atom, the described fluorine-containing luxuriant and rich with fragrance structure such as institute of formula III for quinoxaline and the conjugated polymer of thiophene
Show：
When R1 and R2 are octyloxy, the described fluorine-containing luxuriant and rich with fragrance structure such as formula for quinoxaline and the conjugated polymer of thiophene
Shown in IV：
Fluorine-containing phenanthrene disclosed by the invention enters for quinoxaline and the conjugated polymer of thiophene according to the reaction mechanism mechanism of reaction as follows
OK：
Specific synthesis step is as follows：
(1) the fluorine-containing luxuriant and rich with fragrance preparation for quinoxaline and its derivative
By 5 fluorine-containing 4,7- bis- bromo- 2,1,3- diazosulfide is dissolved in absolute ethyl alcohol, and boron hydrogen is added portionwise at 0 DEG C
Change sodium, 20h is then reacted at room temperature, reaction removes ethanol after terminating with distillation under vacuum, adds suitable quantity of water, ethyl acetate extraction
Take, organic phase is dried with anhydrous magnesium sulfate, crude product obtains fluorinated diamine through silicagel column purifying, then with 2,3- dialkyl group/alcoxyl
11 fluorine-containing bromo- 2,3- dialkyl group/alkoxy quinoxalines of 10,13- bis- are made using acetic acid as solvent reaction in base phenanthrenequione.
(2) the fluorine-containing luxuriant and rich with fragrance preparation for quinoxaline and the D-A type conjugated polymer of thiophene
The reaction is carried out under nitrogen protection, by 11 fluorine-containing bromo- 2,3- dialkyl group/alkoxies of 10,13- bis- of short of electricity unit
The mole of quinoxaline is added to dry two mouthfuls as 2,5- bis- (tin trimethyl) thiophene of matching criterion, and equimolar amounts
In flask, toluene dissolving, fluorine-containing phenanthrene adds 0.02 for the control of quinoxaline monomer concentration after 0.03mol/L or so, ventilation 0.5h
The palladium of catalyst three (dibenzylideneacetone) two and the part tri-o-tolyl phosphorus of 0.08 times of mole of times mole, continue logical
Gas 0.5h, is then begun to warm up, after back flow reaction 24h, stops reaction, and system is cooled to room temperature, and reaction solution is instilled in methanol
Sedimentation, filtering, the polymer of collection dries 12h for 50 DEG C in vacuum drying oven, carries out Soxhlet with methanol, n-hexane, chloroform successively and carries
Take, concentrate chloroform extracted solution, settled again with methanol, filter, obtain fluorine-containing luxuriant and rich with fragrance being total to for quinoxaline and thiophene shown in formula I
Conjugated polymer.
Beneficial effect：
(1) present invention has wider absorption spectrum, and compared with polymer D, absorption spectrum there occurs obvious red shift, effectively
Ground reduces the optical energy gap of polymer；
(2) present invention has HOMO energy levels more deeper than polymer D, -5.67eV can be deep to, applied in photovoltaic cell
Obtain>0.89V high open circuit voltage；
(3) the characteristics of present invention possesses thin pillar and depth HOMO energy levels, has very much to the photovoltaic performance for improving photovoltaic device
With.
Brief description of the drawings
Fig. 1 is polymer A, D abosrption spectrogram.
Fig. 2 is polymer A, D C-V figures.
Fig. 3 is polymer device A, D I-V diagram.
Embodiment
The particular content of the present invention is described in more detail below in conjunction with drawings and examples.
Specific embodiment of the invention given below is, it is necessary to which explanation is that the invention is not limited in implement in detail below
Example, all equivalents done on the basis of technical scheme each fall within protection scope of the present invention.
Embodiment 1：The synthesis of intermediate
(1) preparation of the bromo- 1,2- phenylenediamines (compound 1) of the fluoro- 3,6- bis- of 4-
Fluoro- 4, the 7- bis- bromo- 2 of 5-, 1,3- diazosulfide (5g, 0.016mol) is dissolved in 150ml absolute ethyl alcohols, at 0 DEG C
NaBH4 (11.1g, 0.29mol) is added portionwise, 20h is then reacted at room temperature.After reaction terminates, second is removed with distillation under vacuum
Alcohol, adds 160ml water, and ethyl acetate extraction, saturated common salt water washing organic phase, last anhydrous MgSO4 is dried.Concentration removal has
Machine solvent, with n-hexane/ethyl acetate, (volume ratio is 25 to obtained crude product:1) silica gel column chromatography, obtains fluoro- 3, the 6- bis- of 4-
Bromo- 1,2- phenylenediamines 3.5g, yield 78%.
(2) preparation of (3- octyloxyphenyls) the second diketone of 1,2- bis- (compound 2)
Into CuBr (4.33g, 30.2mmol) THF solution, (40ml) adds LiBr (5.25g, 60.4mmol), room temperature
Temperature is down to 0 DEG C under lower stirring and dissolving, ice bath, starts a RMgBr [bromobenzene octyl ether for bromobenzene octyl ether between dropwise addition brand-new
(8.6g, 30.2mmol), Mg (1g, 41.7mmol), THF (30ml)], react after 20min, start that oxalyl chloride is added dropwise at 0 DEG C
(1.71g, 13.5mmol), completion of dropping continues to react 30min.Saturation NH4Cl solution is added into system reaction, second is quenched
Acetoacetic ester is extracted, salt water washing organic phase, and anhydrous MgSO4 is dried, and concentration removes organic solvent, obtained crude product with just oneself
(volume ratio is 200 to alkane/ethyl acetate:1) silica gel column chromatography, obtains 1,2- bis- (3- octyloxyphenyls) second diketone 3.46g, yield
55%.
(3) preparation of the octyloxy -9,10- phenanthrenequione (compound 3) of 2,7- bis-
Under argon gas protection, 1,2- bis- (3- octyloxyphenyls) second diketone (0.70g, 1.5mmol) is dissolved in 80ml and dries dichloro
In dichloromethane, 0.25ml BFEEs and trifluoro vanadyl (0.41g, 3.3mmol) are added, 0 DEG C is stirred 10 minutes；Add
Molybdenum pentachloride (0.90g, 3.3mmol), stirring reaction 30min.The sodium bicarbonate solution (50ml) of ice is added into system, is taken out
Filter, ethyl acetate extraction, anhydrous magnesium sulfate is dried, and concentration removes organic solvent, obtained crude product n-hexane/ethyl acetate
(volume ratio is 100:1) silica gel column chromatography, obtains octyloxy -9, the 10- phenanthrenequione 0.56g of 2,7- bis-, yield 80%.
(4) preparation of the bromo- octyloxy benzodiazepine * anthracenes (compound 4) of 2,7- bis- of the fluoro- 10,13- bis- of 11-
Bromo- 1, the 2- phenylenediamines (0.59g, 1.9mmol) of fluoro- 3, the 6- bis- of 4- and octyloxy -9, the 10- phenanthrenequione of 2,7- bis-
(0.88g, 1.9mmol) is dissolved in 40ml acetic acid, is warming up to 60 DEG C, closes heating, 2h is reacted at room temperature.Suction filtration, ethanol washing
Filter cake, obtains the bromo- octyloxy benzodiazepine * anthracene 1.28g of 2,7- bis- of fluoro- 10, the 13- bis- of 11-, yield 95%.Nuclear-magnetism characterize data is：
1H NMR(CDCl3,500MHz,ppm),δ:8.40(d,2H),8.04(d,2H),7.84(d,1H),7.15(s,2H),4.09
(t,4H),1.85(s,4H),1.37(m,20H),0.85(s,6H)。
Embodiment 2：Polymer A
Reaction is carried out under nitrogen protection, the bromo- octyloxy benzodiazepine * anthracenes of 2,7- bis- of fluoro- 10, the 13- bis- of 11- (213.7mg,
0.3mmol) it is dissolved in double (tin trimethyl) thiophene (198.6mg, 0.3mmol) of 2,5- in 10ml toluene, leads to nitrogen 0.5h, add
The palladium (5.5mg) of catalyst three (dibenzylideneacetone) two and part tri-o-tolyl phosphorus (9.8mg), are opened after continuing ventilation 0.5h
Begin heating, back flow reaction 24h, system natural cooling at room temperature is added in methanol and settled dropwise, filtering, the polymer of collection
50 DEG C of baking 12h of vacuum drying oven, obtained polymer uses methanol, n-hexane, chloroform surname extraction, concentrates chloroform extracted solution successively,
Drop in methanol and settle again, obtain polymer A 175mg, be atropurpureus fibrous solids, yield 88%, number-average molecular weight
192.38kDa, breadth coefficient 2.94.
Electro-chemical test：With CHI660D type electrochemical workstations, use glass-carbon electrode for working electrode, platinum electrode is
To electrode, Ag/Ag+ electrodes are reference electrode, and Bu4NPF6 makees electrolyte, in acetonitrile solvent, poly- through cyclic voltammetry
The initial oxidation current potential of compound A films is 0.95V, according to calculation formula-(the 4.72+ initial oxidations current potential/V) of HOMO energy levels
EV, the HOMO energy levels for obtaining polymer A are -5.67eV, see accompanying drawing 1,0.16eV is reduced than polymer D.
Photovoltaic performance is studied：Using ITO/PEDOT:PSS/ polymer:PC71BM/PFN/Al sandwich battery structure,
Polymer A and acceptor material PC71BM are compared 1 according to weight:3 are made photovoltaic cell, effective area 0.16cm2, in Newport
Current-voltage test is carried out under the simulated solar light sources of Thermal Oriel 69911, is gathered using the source tables of Keithley 2611,
Open-circuit voltage is 0.92V, short-circuit current density 11.6mA/cm2, and fill factor, curve factor 54.1%, photoelectric transformation efficiency is 5.77%.
Embodiment 3：Polymer B
Be the same as Example 2, the bromo- octyloxy benzodiazepine * anthracenes of 3,6- bis- of fluoro- 10, the 13- bis- of 11- are changed to by short of electricity unit, are used
Identical polymerization obtains polymer B, yield 76%, number-average molecular weight 153.67kDa, breadth coefficient 2.75.
Electro-chemical test：With CHI660D type electrochemical workstations, use glass-carbon electrode for working electrode, platinum electrode is
To electrode, Ag/Ag+ electrodes are reference electrode, and Bu4NPF6 makees electrolyte, in acetonitrile solvent, poly- through cyclic voltammetry
The HOMO of compound B films can be -5.58eV.
Photovoltaic performance is studied：Using ITO/PEDOT:PSS/ polymer:PC71BM/LiF/Al sandwich battery structure,
Photovoltaic cell is made according to certain weight ratio in polymer B and acceptor material PC71BM, effective area 0.16cm2,
Current-voltage test is carried out under the simulated solar light sources of Newport Thermal Oriel 69911, Keithley 2611 is utilized
Source table collection, open-circuit voltage is 0.89V, and photoelectric transformation efficiency is 5.42%.
Embodiment 4：Polymer C
Be the same as Example 3, short of electricity unit is changed to fluoro- 10, the 13- bis- bromo- 2 of 11-, and 3,6,7- bis- octyloxy benzodiazepine * anthracenes are adopted
Polymer C, yield 72%, number-average molecular weight 90.78kDa, breadth coefficient 2.43 are obtained with identical polymerization.
Electro-chemical test：With CHI660D type electrochemical workstations, use glass-carbon electrode for working electrode, platinum electrode is
To electrode, Ag/Ag+Electrode is reference electrode, Bu4N·PF6Make electrolyte, it is poly- through cyclic voltammetry in acetonitrile solvent
The HOMO of compound C films can be -5.63eV.
Photovoltaic performance is studied：Using ITO/PEDOT:PSS/ polymer:PC71BM/PFN/Al sandwich battery structure, will
Polymer C and acceptor material PC71Photovoltaic cell, effective area 0.16cm is made according to certain weight ratio in BM2, in Newport
Current-voltage test is carried out under the simulated solar light sources of Thermal Oriel 69911, is gathered using the source tables of Keithley 2611,
Open-circuit voltage is 0.91V, and photoelectric transformation efficiency is 5.58%.
The HOMO energy levels of the polymer of table 1
Claims (4)
1. a kind of fluorine-containing phenanthrene is for quinoxaline and the conjugated polymer of thiophene, it is characterised in that general structure is as shown in formula I：
In formula, R1、R2Can be with identical also different
Work as R1During=H, R2It is the alkoxy for the straight or branched that carbon number is 4 to 20；
Work as R2During=H, R1It is the alkoxy for the straight or branched that carbon number is 4 to 20；
Work as R1=R2When, it is the alkoxy of 4 to 20 straight or branched.
2. fluorine-containing phenanthrene as claimed in claim 1 is for quinoxaline and the conjugated polymer of thiophene, it is characterised in that described is fluorine-containing
The luxuriant and rich with fragrance structure for quinoxaline and the conjugated polymer of thiophene is as shown in formula II：
。
3. fluorine-containing phenanthrene as claimed in claim 1 is for quinoxaline and the conjugated polymer of thiophene, it is characterised in that described is fluorine-containing
The luxuriant and rich with fragrance structure for quinoxaline and the conjugated polymer of thiophene is as shown in formula III：
。
4. fluorine-containing phenanthrene as claimed in claim 1 is for quinoxaline and the conjugated polymer of thiophene, it is characterised in that described is fluorine-containing
The luxuriant and rich with fragrance structure for quinoxaline and the conjugated polymer of thiophene is as shown in formula IV：
。
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| CN108276559B (en) * | 2018-01-16 | 2020-01-17 | 华南协同创新研究院 | Phenanthro-containing tri-heterocyclic conjugated polymer and application thereof in organic photoelectric device |
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