CN108129447A - A kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application - Google Patents
A kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to organic solar battery material technical fields, and in particular to a kind of Novel Fluorene class organic solar batteries acceptor material and its preparation method and application.The present invention is complicated for existing non-fullerene small molecule receptor material molecule, molecular weight is larger, preparation process is difficult, synthesis material costliness and the shortcomings of being unfavorable for commercial applications, the present invention provides a kind of Novel Fluorene class organic solar batteries acceptor materials, wherein fluorenes class organic solar batteries acceptor material S 1 and S 2 is simple linear structure, molecular structure is simple, molecular weight is small, preparation process is few and it is simple, synthesis material is cheap and easily-available, have good visible absorption range and absorption intensity；The fluorenes class organic solar batteries acceptor material is applied in organic solar batteries photovoltaic device, so that element manufacturing cost is greatly lowered on the basis of ensureing that device obtains good absorption range and absorption intensity, be conducive to organic solar batteries commercial applications early.
Description
Technical field
The invention belongs to organic solar battery material technical fields, and in particular to a kind of Novel Fluorene class organic solar electricity
Pond acceptor material and its preparation method and application.
Background technology
Organic solar batteries (Organic Photovoltaics, referred to as：OPV it is) to grow up the 1980s
A kind of the novel photovoltaic device of opto-electronic conversion effect is realized based on organic semiconductor light absorbent.Research shows that with tradition
Inorganic silicon solar cell is compared, OPV have molecular structure adjustability, cheap, body it is light take, can utilize it is roll-to-roll and
The advantages that spraying printing technique realizes rapid large-area processing flexibility device has obtained extensive concern and has gradually been stepped to industrialization
Into.
The active layer of polymer solar battery usually by the electron donor based on Polymer/Small-Molecules and electronics by
Body is blended.As electron acceptor material, the fullerene n-type organic semiconductor using PCBM as representative extensively should
For in polymer solar battery, the polymer solar battery efficiency based on polymer-fullerene to have broken through 11%.But
Be, due to fullerene receptor there are visual field light absorption compared with it is weak, molecular entergy level modulation range is small, synthesis and cost for purification it is higher
Limitation, people gradually turn to sight based on non-fullerene type polymer solar battery.From Chinese Academy of Sciences's chemistry in 2015
Zhan Xiaowei seminars of key lab of organic solid institute of institute design synthesized using ITIC as representative non-fullerene acceptor material with
Come, the organic solar batteries efficiency based on non-fullerene acceptor has broken through 13%, but none not molecule knot of above-mentioned material at present
Structure is complicated, and molecular weight is larger, and preparation process is difficult, and synthesis material is expensive, is unfavorable for commercial applications.
Invention content
The present invention is in view of the deficiencies of the prior art, and it is an object of the present invention to provide a kind of Novel Fluorene class organic solar batteries receptor material
Material and its preparation method and application.
For achieving the above object, the technical solution adopted by the present invention is：
A kind of Novel Fluorene class organic solar batteries acceptor material, general structure are：
Wherein, m and n is natural number, and the two algebraical sum is more than or equal to 3；
R1 and R2 is alkyl straight-chain or branch of the contained carbon atom number from 1~20；
B1 and B2 is connection electron unit and the bridged linkage between by electronic unit, and structural formula is selected from following knot
Structure：
A1 and A2 is electrophilic unit end group, and structural formula is selected from such as lower structure：
In said program, it is further preferable that the fluorenes class organic solar batteries acceptor material is S-1, structural formula is：
In said program, it is further preferable that the fluorenes class organic solar batteries acceptor material is S-2, structural formula is：
The preparation method of above-mentioned fluorenes class organic solar batteries acceptor material S-1, includes the following steps：
(1) synthesis of compound 1：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2,7- dibromos fluorenes, four fourths
Base ammonium iodide injects DMSO and NaOH solution under nitrogen protection, is heated to 100 DEG C~120 DEG C, reaction overnight, TLC is monitored；
After reaction, it is cooled to room temperature, reaction solution is transferred in separatory funnel, washed with dilute hydrochloric acid, petroleum ether extraction, saturation food
Salt water washing organic phase, organic phase drying concentration, petroleum ether cross pillar, obtain colourless transparent liquid compound 1；The 2,7- bis-
Bromine fluorenes, tetrabutylammonium iodide, DMSO and NaOH solution proportioning are 15mmol：4.5mmol：50ml：30ml；The NaOH solution
Mass concentration is 30%~50%；
(2) synthesis of compound 2：Take twoport round-bottomed flask, anhydrous and oxygen-free processing, sequentially add 2- tributyl tins thiophene,
Compound 1, tetra-triphenylphosphine palladium and dry toluene, are heated to reflux, TLC monitorings；After reaction, reaction solution is directly rotated dense
Contracting, silica gel column chromatography, petroleum ether make eluent, obtain colourless transparent liquid product Compound 2；The 2- tributyl tins thiophene
Fen, compound 1, tetra-triphenylphosphine palladium and dry toluene proportioning are 11mmol：11mmol：0.22mmol：80ml；
(3) synthesis of compound 3：Twoport round-bottomed flask is taken, connects reflux condensing tube, anhydrous and oxygen-free processing, sequentially adding
Close object 2, zinc powder, NiCl2(PPh3)2And tetrabutylammonium iodide；Under nitrogen protection, suck-back enters THF, is heated to reflux, is overnight anti-
Should, TLC monitorings；After reaction, it is cooled to room temperature, is spin-dried for THF, silica gel column chromatography, with petroleum ether:Dichloromethane makees eluant, eluent
Elution, obtains pure compound 3；The compound 2, zinc powder, NiCl2(PPh3)2, tetrabutylammonium iodide and THF proportioning be
0.13mmol：0.2mmol：0.065mmol：0.13mmol：1ml；
(4) synthesis of compound 4：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing adds in compound 3, protected in nitrogen
Under, suck-back enters THF, and 15min~20min is stirred at -78 DEG C, instills n-BuLi dropwise, the reaction was continued 1h~1.5h；Syringe is noted
DMF is done in the excess of imports, rapid to sample, and TLC monitorings are subsequently injected into methanol, are transferred to room temperature, add in a large amount of distilled water and be quenched, warm table
On be stirred at room temperature；After reaction, system being transferred to separatory funnel, dichloromethane extraction is dry, concentrates, silica gel column chromatography,
With petroleum ether:Ethyl acetate as eluent elutes, and obtains yellow solid compound 4；The compound 3, n-BuLi, DMF and THF
It matches as 0.3mmol：1.2mmol：2.4mmol：30ml；
(5) synthesis of acceptor material S-1：Two-neck bottle is taken, connects reflux condensing tube, anhydrous and oxygen-free processing；Addition compound 4,
1,1- methylene dicyanoethyl -3- indones, under nitrogen atmosphere, syringe injection chloroform, pyridine are heated to reflux, reaction overnight, TLC
Monitoring；After reaction, it is cooled to room temperature, directly concentrates, chloroform dissolving, chloroform crosses pillar, removes unilateral product；Petroleum ether/
Dichloromethane system recrystallizes, and finally obtains acceptor material S-1；The compound 4,1,1- methylene dicyanoethyl -3- indones, pyridine
It is 0.2mmol with chloroform proportioning：0.6mmol：1.2ml：50ml.
The preparation method of above-mentioned fluorenes class organic solar batteries acceptor material S-2, includes the following steps：
(1) synthesis of compound 1：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2,7- dibromos fluorenes, four fourths
Base ammonium iodide injects DMSO and NaOH solution under nitrogen protection, is heated to 100 DEG C~120 DEG C, reaction overnight, TLC is monitored；
After reaction, it is cooled to room temperature, reaction solution is transferred in separatory funnel, washed with dilute hydrochloric acid, petroleum ether extraction, saturation food
Salt water washing organic phase, organic phase drying concentration, petroleum ether cross pillar, obtain colourless transparent liquid compound 1；The 2,7- bis-
Bromine fluorenes, tetrabutylammonium iodide, DMSO and NaOH solution proportioning are 15mmol：4.5mmol：50ml：30ml；The NaOH solution
Mass concentration is 30%~50%；
(2) synthesis of compound 2：Take twoport round-bottomed flask, anhydrous and oxygen-free processing, sequentially add 2- tributyl tins thiophene,
Compound 1, tetra-triphenylphosphine palladium and dry toluene, are heated to reflux, TLC monitorings；After reaction, reaction solution is directly rotated dense
Contracting, silica gel column chromatography, petroleum ether make eluent, obtain colourless transparent liquid product Compound 2；The 2- tributyl tins thiophene
Fen, compound 1, tetra-triphenylphosphine palladium and dry toluene proportioning are 11mmol：11mmol：0.22mmol：80ml；
(3) synthesis of compound 5：Two-neck bottle is taken, anhydrous and oxygen-free processing adds in compound 1 and anhydrous THF, -78 DEG C of stirrings
N-BuLi is added dropwise in 15min~20min, is stirred to react；That borate of addition isopropanol, closes system after reaction 1.5h~2h
It is cold, reaction overnight, TLC monitorings；Stop reaction after reacting 9h~12h, water quenching is added to go out, dichloromethane extraction, dry concentration, silica gel
Column chromatography makees eluent with petrol ether/ethyl acetate, obtains pure white solid product Compound 5；The compound 1, n-
That borate of BuLi, isopropanol and THF proportionings are 16mmol：40mmol：64mmol：100ml；
(4) synthesis of compound 6：Two-neck bottle is taken, anhydrous and oxygen-free processing sequentially adds compound 5, compound 2, four triphens
Base phosphine palladium and Anhydrous potassium carbonate under nitrogen protection, inject dry toluene and distilled water, are heated to reflux, reaction overnight, TLC prisons
It surveys；After reaction, it is cooled to room temperature, dichloromethane extraction, organic phase drying concentration, silica gel column chromatography, with petroleum ether/acetic acid
Ethyl ester makees eluent, crosses column and obtains compound 6；The compound 5, compound 2, tetra-triphenylphosphine palladium, Anhydrous potassium carbonate,
Distilled water and dry toluene proportioning are 2mmol：4.4mmol：0.06mmol：80mmol：12ml：30ml；
(5) synthesis of compound 7：Two-neck bottle is taken, anhydrous and oxygen-free processing adds in compound 6, under nitrogen atmosphere, suck-back
THF stirs 15min~20min at -78 DEG C, and n-BuLi is added dropwise in syringe dropwise, continues to stir 1h~1.5h, be dripped with syringe
Add super dry DMF, the reaction was continued 5min~10min, stopping reaction；After reaction, it adds in methanol and reaction is quenched, then from -78
Reaction bulb is taken out under DEG C environment, adds in a large amount of deionized waters, is placed on after being stirred on reaction bench, reaction mixture is poured into liquid separation leakage
In bucket, dichloromethane extraction, organic phase drying, concentration, silica gel column chromatography, with petroleum ether:Dichloromethane makees eluent, obtains
To dark green solid product Compound 7；The compound 6, n-BuLi, DMF and THF proportioning are 0.45mmol：1.8mmol：
3.6mmol：30ml；
(6) synthesis of acceptor material S-2：Two-neck bottle is taken, connects reflux condensing tube, anhydrous and oxygen-free is handled, addition compound 7,
1,1- methylene dicyanoethyl -3- indones, under nitrogen atmosphere, syringe injection chloroform, pyridine are heated to reflux, reaction overnight, TLC
Monitoring；After reaction, stop heating, be cooled to room temperature, directly concentrate, chloroform dissolving, chloroform is crossed pillar, removed unreacted
The unilateral impurity of indigo ketone and part, obtained acceptor material S-2 crude products, after S-2 crude products are dissolved in dichloromethane, in dichloro
Petroleum ether is gently spread on methane liquid level, it is overnight, it filters, the solid that petroleum ether filters out obtains pure dark brown chromogenic receptor material
Expect S-2；The compound 7,1,1- methylene dicyanoethyl -3- indones, pyridine and chloroform proportioning are 0.25mmol：0.75mmol：
1.5ml：50ml.
Application of the above-mentioned fluorenes class organic solar batteries acceptor material in organic solar batteries；Specifically, it is described to have
Machine solar cell, acceptor material be above-mentioned fluorenes class organic solar batteries acceptor material, donor material PTB7-Th, institute
The structural formula for stating PTB7-Th is
Beneficial effects of the present invention are as follows：1) it is complicated for existing non-fullerene small molecule receptor material molecule, point
Son amount is larger, and preparation process is difficult, and synthesis material costliness and the shortcomings of being unfavorable for commercial applications, the present invention provides a kind of new
Type fluorenes class organic solar batteries acceptor material, wherein fluorenes class organic solar batteries acceptor material S-1 and S-2 is simple line
Property structure, molecular structure is simple, molecular weight is small, preparation process is few and it is simple, synthesis material is cheap and easily-available, have it is good visible
Light abstraction width and absorption intensity；The fluorenes class organic solar batteries acceptor material is applied to organic solar batteries photovoltaic
In device, so that element manufacturing cost significantly drops on the basis of ensureing that device obtains good absorption range and absorption intensity
It is low, be conducive to organic solar batteries commercial applications early；2) it is prepared for the prior art using Yamamoto methods from even
Using expensive double-(1,5- cyclo-octadiene) nickel as reaction raw materials during co-product, the present invention is coupled preparation certainly using Liv Ullmann
From coupling intermediate product, synthesis cost, the system of fluorenes class organic solar batteries the acceptor material S-1 and S-2 are greatly reduced
Preparation Method is simple, and synthesis material is cheap and easily-available.
Description of the drawings
Fig. 1 is the synthetic route chart of acceptor material S-1 that embodiment 1 is prepared.
Fig. 2 is the synthetic route chart of acceptor material S-2 that embodiment 2 is prepared.
Fig. 3 is that normalization of the acceptor material S-1 that is prepared of embodiment 1 respectively under weak solution and filminess is purple
Outside-visible absorption spectra figure.
Fig. 4 is that normalization of the acceptor material S-2 that is prepared of embodiment 2 respectively under weak solution and filminess is purple
Outside-visible absorption spectra figure.
Fig. 5 is two kinds of acceptor material S-1 and normalization UV-visible absorption spectrums of the S-2 under filminess.
Fig. 6 is the electrochemistry cyclic voltammetry curve figure of two kinds of acceptor materials S-1 and S-2.
Fig. 7 is that structure is ITO/PEDOT:PSS/ polymer Ps TB7-Th/S-n (1:1.5) polymer solar of/Ca/Al
The current -voltage curve figure of cell photovoltaic device.
Fig. 8 is that structure is ITO/PEDOT:PSS/ polymer Ps TB7-Th/S-1 (1:1,1:1.5,1:2) polymerization of/Ca/Al
The current -voltage curve figure of object solar cell photovoltaic device.
It is structure is ITO/PEDOT that Fig. 9, which is Fig. 9,:PSS/ polymer Ps TB7-Th/S-2 (1:1,1:1.5,1:2)/Ca/Al
Polymer solar battery photovoltaic device current -voltage curve figure.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention
Content is not limited solely to the following examples.
The petroleum ether that is used in following embodiment, dichloromethane, ethyl acetate, chloroform, toluene, tetrahydrofuran, without water beetle
Alcohol, sodium hydroxide, dilute hydrochloric acid, Anhydrous potassium carbonate, chromatographic silica gel are purchased from Wuhan Shen Shi Chemical Co., Ltd.s；Anhydrous N, N- dimethyl
Formamide, n-BuLi, tetra-triphenylphosphine palladium, two triphenylphosphine nickel chlorides, anhydrous DMSO, bromo n-decane are purchased from Shanghai lark
Waffle Technology Co., Ltd.；2,7- dibromos fluorenes, tetrabutylammonium iodide, thiophene, zinc powder, anhydrous pyridine, isopropanol that borate
It is purchased from Shanghai Aladdin biochemical technology limited company；1,1- methylene dicyanoethyl -3- indones are prepared by laboratory internal.More than
Toluene, tetrahydrofuran carry out anhydrous and oxygen-free processing again in buying reagent, and other reagents directly use.
The preparation method of 2- tributyl tin thiophene is as follows：Take 250ml twoport round-bottomed flasks, constant pressure funnel, anhydrous nothing
Oxygen processing, vacuumizes, suck-back enters THF (100ml), N2Under protection with syringe injection thiophene (120mmol, 10.92g), -78 DEG C
Under n-BuLi (100mmol, 40ml) is added dropwise dropwise, 1h is stirred to react after dripping, then adds in tributyltin chloride
(105mmol, 34.2g) stops refrigeration, reaction overnight.Post processing：Water quenching is added to go out, is spin-dried for THF, petroleum ether extraction is dry dense
Contracting, distillation, obtains weak yellow liquid product 2- tributyl tins thiophene (95mmol, 35.5g), yield 91%.
Embodiment 1
A kind of fluorenes class organic solar batteries acceptor material S-1, chemical structural formula are：
Above-mentioned fluorenes class organic solar batteries acceptor material S-1, preparation method are following (preparation route is as shown in Figure 1)：
(1) synthesis of compound 1：250ml twoport round-bottomed flasks are taken, anhydrous and oxygen-free processing sequentially adds 2,7- dibromo fluorenes
(15mmol), tetrabutylammonium iodide (30wt%, 4.5mmol) take out inflated with nitrogen 3 times, the lower injection 50ml DMSO of nitrogen protection and
30ml 50wt%NaOH solution is heated to 100 DEG C, and reaction overnight, TLC is monitored；Post processing：Reaction stops, and is cooled to room temperature,
It is transferred in 500ml separatory funnels, 100ml 10% (volumetric concentration) dilute hydrochloric acid washing (being slowly added to, CARE Exotherm is violent),
Petroleum ether extraction, saturated salt solution 50ml*3 washing organic phases, organic phase drying concentration, petroleum ether are crossed pillar, are obtained colourless
Prescribed liquid compound 1 (14mmol), yield 95%,1HNMR (500MHz, CDCl3, δ), 7.51 (d, J=7.1Hz, 2H), 7.45
(d, J=6.8Hz, 4H), 1.91 (m, 4H), 1.27-1.05 (m, 32H), 0.87-0.84 (m, 6H)13CNMR(125MHz,
CDCl3,)152.58,139.08,130.16,126.20,121.48,121.10,77.27,77.02,76.76,55.70,
40.15,31.87,29.87,29.51,29.27,29.20,23.65,22.66,14.10；
(2) synthesis of compound 2：100ml twoport round-bottomed flasks are taken, anhydrous and oxygen-free processing sequentially adds 2- tributyl tins
Thiophene (1eq, 11mmol), compound 1 (11mmol), tetra-triphenylphosphine palladium (2%eq, 0.22mmol) and 80ml dry toluenes,
It is heated to reflux, TLC monitorings；Post processing：Direct concentrated by rotary evaporation, silica gel column chromatography, petroleum ether make eluant, eluent, obtain water white transparency liquid
Body product Compound 2 (6.6mmol), yield 60%,1HNMR (500MHz, CDCl3, δ) 7.68 (d, J=5Hz, 1H), 7.62
(d, J=10Hz, 1H), 7.57 (d, J=10Hz, 2H), 7.48 (d, J=5Hz, 2H), 7.41 (d, J=5Hz, 1H), 7.33 (d,
J=5Hz, 1H), 7.13 (m, 1H), 2.04-1.93 (m, 4H), 1.31-1.08 (m, 32H), 0.88-0.85 (m, 6H)13CNMR
(125MHz,CDCl3,δ)153.17,151.55,151.20,150.92,145.28,144.99,140.75,140.68,
133.21,130.06,128.91,128.90,128.04,127.13,126.84,126.20,125.99,125.09,124.89,
124.69,124.44,123.05,122.90,122.84,120.21,120.18,120.06,119.72,77.31,77.06,
76.81,55.54,55.19,40.42,40.32,31.91,29.59,29.56,29.31,23.79,23.74,22.75,
22.70,14.14；
(3) synthesis of compound 3：10ml twoport round-bottomed flasks are taken, connect reflux condensing tube, anhydrous and oxygen-free processing adds successively
Enter compound 2 (0.13mmol), zinc powder (1.5eq, 0.2mmol, 0.013g), NiCl2(PPh3)2(50%eq, 0.065mmol,
0.0425g), tetrabutylammonium iodide (1eq, 0.13mmol, 0.048g)；Take out inflated with nitrogen 3 times, suck-back enters THF (1ml), heats back
Stream, reaction overnight, TLC monitorings；Post processing：Stop heating, be cooled to room temperature, be spin-dried for THF, silica gel column chromatography, petroleum ether：Dichloro
Methane=30:1 makees eluant, eluent, obtains pure compound 3 (0.046mmol, 48mg), yield 70%,1HNMR (500MHz,
CDCl3, δ) 7.80 (d, J=7.5Hz, 2H), 7.75 (d, J=8Hz, 2H), 7.68-7.62 (m, 8H), 7.42 (d, J=3Hz,
2H), 7.32 (d, J=5Hz, 2H), 7.15 (m, 2H), 2.10-2.05 (m, 8H), 1.28-1.11 (m, 64H), 0.87-0.84
(m,12H).13CNMR(125MHz,CDCl3,δ)148.32,148.21,141.23,141.01,139.90,138.23,
133.11,130.15,130.52,129.44,128.91,125.57,124.70,53.48,43.98,31.95,30.26,
29.67,29.33,24.44,22.70,14.13；
(4) synthesis of compound 4：100ml twoport round-bottomed flasks are taken, anhydrous and oxygen-free processing adds in compound 3
(0.3mmol), pumping fill N23 times, suck-back enters THF (30ml), and 15min is stirred at -78 DEG C, dropwise instill n-BuLi (4eq,
1.2mmol, 0.5ml), reaction system becomes bottle green emulsion by faint yellow quickly, the reaction was continued 1h；Syringe injection is super dry
DMF (8eq, 2.4mmol, 0.2ml), reaction system quickly become yellow emulsion, rapid to sample TLC monitorings, are injected after 5min
Methanol 10ml, is transferred to room temperature, adds in a large amount of distilled water and is quenched, 5min is stirred at room temperature on warm table；Post processing：System is shifted
To 250ml separatory funnels, dichloromethane extraction, dry, concentration, silica gel column chromatography, petroleum ether：Ethyl acetate=5:1 elutes
Agent, obtains yellow solid compound 4 (0.21mmol), yield 70%,1HNMR (500MHz, CDCl3, δ) 9.95 (s, 2H),
7.85-7.80 (m, 6H), 7.74-7.67 (m, 8H), 7.52 (d, J=4Hz, 2H), 2.12-2.10 (m, 8H), 1.29-1.12
(m,64H),0.87-0.84(m,12H).13CNMR(125MHz,CDCl3,δ)182.68,155.20,152.16,152.01,
142.40,142.05,141.04,139.50,137.47,131.76,126.41,125.62,123.82,121.51,120.74,
120.42,77.30,77.04,76.79,55.48,40.29,31.87,29.55,29.53,29.28,29.23,23.86,
22.65,14.09.
(5) synthesis of acceptor material S-1：100ml two-neck bottles are taken, connect reflux condensing tube, anhydrous and oxygen-free processing；Add in chemical combination
Object 4 (0.2mmol), 1,1- methylene dicyanoethyl -3- indones (3eq, 0.6mmol), take out inflated with nitrogen 3 times, syringe injection chloroform
(50ml), pyridine (1.2ml), is heated to reflux, reaction overnight, TLC monitorings；Post processing：Stop heating, be cooled to room temperature, directly
Concentration, chloroform dissolving, chloroform cross pillar, remove unilateral product；Petroleum ether/dichloromethane system recrystallization, finally obtains receptor
Material S-1 (200mg, 0.14mmol), yield 70%；1HNMR (500MHz, CDCl3, δ) 8.91 (d, J=2Hz, 2H), 8.72-
8.71 (m, 2H), 7.98 (d, J=6.5Hz, 2H), 7.91-7.83 (m, 10H), 7.78-7.71 (m, 8H), 7.62 (d, J=
3.5Hz,2H),2.62(m,8H),1.24-1.13(m,64H),0.85-0.83(m,12H).13CNMR(125MHz,CDCl3,δ)
188.40,161.53,152.35,152.24,146.49,143.25,141.25,140.03,139.53,136.24,134.55,
131.81,124.85,121.55,120.92,120.57,114.57,114.48,77.32,77.07,76.81,69.77,
55.67,40.32,31.88,29.99,29.59,29.55,29.30,23.92,22.65,14.10。
Embodiment 2
A kind of fluorenes class organic solar batteries acceptor material S-2, chemical structural formula are：
Above-mentioned fluorenes class organic solar batteries acceptor material S-2, preparation method are following (preparation route is as shown in Figure 2)：
(1) synthesis of compound 1 and compound 2 is the same as embodiment 1；
(2) synthesis of compound 5：Take 250ml two-neck bottles, anhydrous and oxygen-free processing, add in compound 1 (16mmol) and
The anhydrous THF of 100ml, -78 DEG C are stirred 15min, and n-BuLi (2.5eq, 16ml, 40mmol) is added dropwise, is stirred to react；Reaction
That borate (4eq, 64mmol) of addition isopropanol after 1.5h closes refrigeration, reaction overnight, TLC monitorings；Post processing：Stop after 9h
It only reacts, water quenching is added to go out, dichloromethane extraction, dry concentration, silica gel column chromatography, petrol ether/ethyl acetate=20/1 elutes
Agent, obtains pure white solid product Compound 5 (13.3mmol), yield 83%,1HNMR (500MHz, CDCl3, δ) 7.83 (d, J
=3.75Hz, 2H), 7.75 (m, 4H), 2.03-2.00 (m, 4H), 1.41 (s, 24H), 1.28-1.03 (m, 32H), 0.88-
0.85(m,6H).13CNMR(125MHz,CDCl3,δ)150.49,143.93,133.69,128.95,127.90,126.96,
126.67,123.04,122.94,119.38,83.71,83.62,77.29,77.04,76.78,55.19,55.09,54.90,
40.25,40.14,31.88,30.01,29.59,29.53,29.27,29.25,24.96,23.69,22.66,22.29,
14.10,13.99；
(3) synthesis of compound 6：250ml two-neck bottles are taken, anhydrous and oxygen-free processing sequentially adds compound 5 (2mmol), changes
Close object 2 (2.2eq, 4.4mmol), tetra-triphenylphosphine palladium (3%eq, 0.06mmol70mg) and Anhydrous potassium carbonate (11g,
80mmol), inflated with nitrogen is taken out 3 times, the lower injection 30ml dry toluenes of nitrogen protection and 12ml distilled water are heated to reflux, reaction overnight,
TLC is monitored.It is cooled to room temperature, dichloromethane extraction, organic phase drying concentration, silica gel column chromatography, petrol ether/ethyl acetate=
50/1 makees eluant, eluent, crosses column and obtains compound 6 (0.6mmol), yield 30%,1HNMR (500MHz, CDCl3,δ),7.85(d,J
=8Hz, 2H), 7.81 (d, J=8Hz, 2H), 7.76 (d, J=8Hz, 2H), 7.71-7.63 (m, 12H), 7.43 (d, J=3Hz,
2H), 7.33 (d, J=5Hz, 2H), 7.16-7.14 (m, 2H), 2.15-2.04 (m, 12H), 1.26-1.12 (m, 96H), 0.88-
0.85(m,18H).13CNMR(125MHz,CDCl3,δ)148.28,141.13,141.02,140.33,139.94,139.90,
133.12,130.57,130.11,128.88,128.61,128.04,127.63,125.59,124.71,53.55,43.93,
31.90,30.28,29.65,29.37,24.44,22.70,14.11；
(4) synthesis of compound 7：250ml two-neck bottles are taken, anhydrous and oxygen-free processing adds in compound 6 (0.45mmol), takes out
Inflated with nitrogen 3 times, suck-back THF (30ml) stir 15min at -78 DEG C, syringe be added dropwise dropwise n-BuLi (4eq, 1.8mmol,
0.72ml), continue to stir 1h, reaction system can be observed, green emulsion is become by green clear solution, be added dropwise with syringe
Super dry DMF (8eq, 3.6mmol, 0.31ml), reaction system become dense green emulsion, reaction 5min or so at once
Stop reaction.Post processing：It adds in methanol and reaction is quenched, then take out reaction bulb under -78 DEG C of environment, add in a large amount of deionizations
Water is placed on reaction bench and stirs 2min, and reaction mixture is poured into separatory funnel, dichloromethane extraction, and organic phase drying is dense
Contracting, silica gel column chromatography, petroleum ether：Dichloromethane=5：1 makees eluant, eluent, obtains dark green solid product Compound 7
(0.28mmol), yield 60%,1HNMR (500MHz, CDCl3,δ),9.95(s,2H),7.86-7.80(m,8H),7.74-7.68
(m,12H),7.53-7.51(m,2H),2.15-2.10(m,12H),1.26-1.12(m,96H),0.87-0.84(m,18H)
.13CNMR(125MHz,CDCl3,δ)182.70,155.27,152.15,151.97,151.88,142.49,142.01,
141.29,139.31,137.48,131.68,126.36,126.23,125.60,123.80,121.51,120.73,120.38,
120.05,77.28,77.03,76.77,55.46,55.38,40.31,31.87,29.97,29.59,29.55,29.53,
29.28,29.24,22.65,14.09；
(5) synthesis of acceptor material S-2：100ml two-neck bottles are taken, connect reflux condensing tube, anhydrous and oxygen-free processing.Add in chemical combination
Object 7 (0.25mmol), 1,1- methylene dicyanoethyl -3- indones (3eq, 0.75mmol), take out inflated with nitrogen 3 times, syringe injection chloroform
(50ml), pyridine (1.5ml), is heated to reflux, reaction overnight, TLC monitorings.Post processing：Stop heating, be cooled to room temperature, directly
Concentration, chloroform dissolving, chloroform cross pillar, remove the unilateral impurity of unreacted indigo ketone and part, and obtained acceptor material S-2 is slightly produced
Object after adding in the dissolving completely of 20ml dichloromethane, is statically placed in draught cupboard, 30ml oil is gently spread on dichloromethane liquid level
Ether, it is overnight, it filters, the solid that petroleum ether filters out obtains pure brownish black acceptor material S-2 (270mg), yield 60%,1HNMR (500MHz, CDCl3, δ), 8.95 (s, 2H), 8.75 (d, J=7.5Hz, 2H), 8.01 (d, J=6.5Hz, 2H), 7.94
(d, J=4Hz, 2H), 7.90-7.78 (m, 14H), 7.75-7.70 (m, 8H), 7.64 (d, J=4Hz, 2H), 2.16-2.15 (m,
12H),1.25-1.13(m,96H),0.86-0.84(m,18H).13CNMR(125MHz,CDCl3,δ)188.42,161.63,
160.48,152.34,152.19,151.93,143.37,140.29,140.22,140.06,136.95,136.22,134.55,
131.73,124.84,122.34,121.55,120.51,114.59,114.50,77.31,77.05,76.80,69.75,
55.65,55.41,40.35,31.89,29.59,29.55,29.30,23.98,23.92,22.66,14.10。
The optical property and chemical property of two kinds of acceptor materials prepared by embodiment 1 and embodiment 2 are referring to the following table 1 and figure
3rd, Fig. 4, Fig. 5, Fig. 6.Table 1 lists the optical property and chemical property parameter of two kinds of acceptor materials.
The optical property of 1 acceptor material of table and chemical property parameter
| Acceptor material | λsolution(nm) | λfilm(nm) | Egap opt(eV) | Eox onset(V) | HOMO(eV) | LUMO(eV) |
| S-1 | 573 | 588 | 1.87 | 1.01 | -5.71 | -3.84 |
| S-2 | 568 | 581 | 1.89 | 1.1 | -5.80 | -3.91 |
Table 1 lists maximum absorption wavelength, optical band gap and LUMO and HOMO energy levels of acceptor material S-1 and S-2 etc.
Optical property and chemical property parameter.Fig. 3 and Fig. 4 is respectively acceptor material S-1 and S-2 respectively in weak solution and filminess
Under normalization UV-visible absorption spectrum, from Fig. 3 and Fig. 4 it can be seen that, long wave under acceptor material S-1 filminesses
Wavelength residing for the maximum absorption band of strong point is 588nm, the 573nm under being absorbed compared to solution, red shift 15nm；Acceptor material S-2
Wavelength residing for the maximum absorption band of long wave strong point is 581nm under filminess, compared to the 568nm under solution absorption, red shift
13nm.This illustrates that acceptor material S-1 and S-2 have relatively stronger intermolecular interaction in the solid state, leads to small point
π-π stack closer orderly under sub- coherent condition.Fig. 5 is that normalization of the two kinds of acceptor material S-1 and S-2 under filminess is purple
Outside-visible absorption spectra figure can intuitively find out S-2 under filminess residing for the maximum absorption band of long wave strong point from figure
Wavelength is 581nm, compared to the 7nm of the 588nm blue shifts residing for S-1；This explanation, although S-2 has longer π-π relative to S-1
Conjugated structure, but in the collected state, the space structure of S-2 has the steric hindrance of bigger, is unfavorable for intermolecular π-π and stacks.
Meanwhile by formula Egap opt=1240/ λonsetIt can obtain their optical band gap Egap optRespectively 1.87eV and 1.89eV.Figure
The 6 electrochemistry cyclic voltammetry curve figure for two kinds of acceptor materials S-1 and S-2, by using electrochemical cyclic voltammetry measure by
The oxidation-reduction process of body material can obtain initial oxidation reduction potential of the acceptor material relative to Ag/Ag+, as shown in Figure 6 by
The initial oxidation current potential of body material S-1 and S-2 are respectively 1.01V and 1.1V.According to formula HOMO=-4.7-EOX,onsetSo as to
It is respectively -5.71eV and -5.80eV, then by formula LUMO=HOMO+ to calculate the HOMO energy levels of acceptor material S-1 and S-2
Egap optIt is respectively -3.84eV and -3.91eV that their lumo energy, which can be calculated,.
PTB7-Th is used as donor material, S-n (n is 1 or 2) is acceptor material, according to ITO/PEDOT:PSS/ polymerize
Object PTB7-Th/S-n (1:1,1:1.5,1:The performance for the solar cell that 2wt/wt)/Ca/Al is fabricated to, referring to the following table 2 and figure
7th, Fig. 8, Fig. 9.Table 2 list in the active layer of solar cell photovoltaic device polymer P TB7-Th respectively with two kinds of receptor materials
The photovoltaic performance parameter that material S-n batteries in the case of different ratio show.
The photovoltaic performance parameter of 2 solar cell of table
| Active layer | Voc(V) | Jsc(mA/cm2) | FF | PCE (%) |
| PTB7-Th:S-1=1:1 | 0.75 | 7.45 | 0.33 | 1.84 |
| PTB7-Th:S-1=1:1.5 | 0.92 | 9.85 | 0.39 | 3.49 |
| PTB7-Th:S-1=1:2 | 0.88 | 5.44 | 0.37 | 1.76 |
| PTB7-Th:S-2=1:1 | 0.86 | 6.59 | 0.33 | 1.87 |
| PTB7-Th:S-2=1:1.5 | 0.83 | 6.72 | 0.36 | 2.01 |
| PTB7-Th:S-2=1:2 | 0.91 | 4.27 | 0.33 | 1.28 |
It is ITO/PEDOT that table 2, which is listed based on structure,:PSS/ polymer Ps TB7-Th/S-n (1:1,1:1.5,1:2)/Ca/
Open-circuit voltage, short circuit current, fill factor and photoelectric conversion efficiency of polymer solar battery photovoltaic device of Al etc. are main
Photovoltaic performance parameter, Fig. 7 are that structure is ITO/PEDOT:PSS/ polymer Ps TB7-Th/S-n (1:1.5) polymer of/Ca/Al
The current -voltage curve figure of solar cell photovoltaic device.The figure shows PTB7-Th in active layer:Acceptor material S-n is most
Excellent proportioning 1:In the case of 1.5, the current -voltage curve figure of photovoltaic device；During using S-1 as acceptor material, the short circuit electricity of device
Stream and open-circuit voltage are respectively 9.85mA/cm2And 0.92V；During using S-2 as acceptor material, the short circuit current of device and open circuit electricity
Pressure is respectively 6.72mA/cm2And 0.83V.Fig. 8 is that structure is ITO/PEDOT:PSS/ polymer Ps TB7-Th/S-1 (1:1,1:
1.5,1:2) the current -voltage curve figure of the polymer solar battery photovoltaic device of/Ca/Al, the figure shows in active layer
PTB7-Th:S-1 is in the case of different ratio, the current -voltage curve figure of photovoltaic device, it is seen that work as PTB7-Th:S-1=1:
When 1.5, the short circuit current and open-circuit voltage of device are maximum, respectively 9.85mA/cm2And 0.92V.Fig. 9 is that structure is ITO/
PEDOT:PSS/ polymer Ps TB7-Th/S-2 (1:1,1:1.5,1:2) the polymer solar battery photovoltaic device of/Ca/Al
Current -voltage curve figure, the figure shows PTB7-Th in active layer:S-2 is in the case of different ratio, the electricity of photovoltaic device
Stream-voltage curve, it is seen that work as PTB7-Th:S-2=1:When 1.5, the short circuit current and open-circuit voltage of device are maximum, respectively
6.72mA/cm2And 0.83V.
Obviously, above-described embodiment is only intended to clearly illustrate made example, and is not the limitation to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And the obvious variation or change therefore amplified
It moves within still in the protection domain of the invention.
Claims (7)
1. a kind of Novel Fluorene class organic solar batteries acceptor material, which is characterized in that the fluorenes class organic solar batteries by
Body material is the non-fullerene organic solar batteries acceptor material of linear type with A-D-A structures, and general structure is：
Wherein, m and n is natural number, and the two algebraical sum is more than or equal to 3；
R1 and R2 is alkyl straight-chain or branch of the contained carbon atom number from 1~20；
B1 and B2 is connection electron unit and the bridged linkage between by electronic unit, and structural formula is selected from such as lower structure：
A1 and A2 is electrophilic unit end group, and structural formula is selected from such as lower structure：
2. fluorenes class organic solar batteries acceptor material according to claim 1, which is characterized in that the fluorenes class is organic too
It is positive can the structural formula of battery acceptor material be：
3. fluorenes class organic solar batteries acceptor material according to claim 1, which is characterized in that the fluorenes class is organic too
It is positive can the structure of battery acceptor material be：
4. the preparation method of fluorenes class organic solar batteries acceptor material described in claim 2, which is characterized in that including walking as follows
Suddenly：
(1) synthesis of compound 1：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2,7- dibromos fluorenes, tetrabutyl iodine
Change ammonium, inject DMSO and NaOH solution under nitrogen protection, be heated to 100 DEG C~120 DEG C, reaction overnight, TLC is monitored；Reaction
After, it is cooled to room temperature, reaction solution is transferred in separatory funnel, washed with dilute hydrochloric acid, petroleum ether extraction, saturated salt solution
Organic phase is washed, organic phase drying concentration, petroleum ether cross pillar, obtain colourless transparent liquid compound 1；
(2) synthesis of compound 2：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2- tributyl tins thiophene, chemical combination
Object 1, tetra-triphenylphosphine palladium and dry toluene, are heated to reflux, TLC monitorings；After reaction, by the direct concentrated by rotary evaporation of reaction solution,
Silica gel column chromatography, petroleum ether make eluent, obtain colourless transparent liquid product Compound 2；
(3) synthesis of compound 3：Twoport round-bottomed flask is taken, connects reflux condensing tube, anhydrous and oxygen-free processing sequentially adds compound
2nd, zinc powder, NiCl2(PPh3)2And tetrabutylammonium iodide；Under nitrogen protection, suck-back enters THF, is heated to reflux, reaction overnight, TLC
Monitoring；After reaction, it is cooled to room temperature, is spin-dried for THF, silica gel column chromatography, with petroleum ether:Dichloromethane does eluent,
Obtain pure compound 3；
(4) synthesis of compound 4：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing adds in compound 3, under nitrogen protection,
THF is sucked, 15min~20min is stirred at -78 DEG C, instills n-BuLi dropwise, the reaction was continued 1h~1.5h；Syringe injection is super
Dry DMF, rapid to sample, TLC monitorings are then injected into methanol, are transferred to room temperature, add in a large amount of distilled water and be quenched, warm table upper chamber
Temperature stirring；After reaction, system is transferred to separatory funnel, dichloromethane extraction, dry, concentration, silica gel column chromatography, with stone
Oily ether:Ethyl acetate as eluent elutes, and obtains yellow solid compound 4；
(5) synthesis of acceptor material S-1：Two-neck bottle is taken, connects reflux condensing tube, anhydrous and oxygen-free processing；Add in compound 4,1,1-
Methylene dicyanoethyl -3- indones, under nitrogen atmosphere, syringe injection chloroform, pyridine are heated to reflux, reaction overnight, TLC monitorings；
After reaction, it is cooled to room temperature, directly concentrates, chloroform dissolving, chloroform crosses pillar, removes unilateral product；Petroleum ether/dichloromethane
Alkane system recrystallizes, and finally obtains acceptor material S-1.
5. the preparation method of fluorenes class organic solar batteries acceptor material described in claim 3, which is characterized in that including walking as follows
Suddenly：
(1) synthesis of compound 1：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2,7- dibromos fluorenes, tetrabutyl iodine
Change ammonium, inject DMSO and NaOH solution under nitrogen protection, be heated to 100 DEG C~120 DEG C, reaction overnight, TLC is monitored；Reaction
After, it is cooled to room temperature, reaction solution is transferred in separatory funnel, washed with dilute hydrochloric acid, petroleum ether extraction, saturated salt solution
Organic phase is washed, organic phase drying concentration, petroleum ether cross pillar, obtain colourless transparent liquid compound 1；
(2) synthesis of compound 2：Twoport round-bottomed flask is taken, anhydrous and oxygen-free processing sequentially adds 2- tributyl tins thiophene, chemical combination
Object 1, tetra-triphenylphosphine palladium and dry toluene, are heated to reflux, TLC monitorings；After reaction, by the direct concentrated by rotary evaporation of reaction solution,
Silica gel column chromatography, petroleum ether make eluent, obtain colourless transparent liquid product Compound 2；
(3) synthesis of compound 5：Two-neck bottle is taken, anhydrous and oxygen-free processing adds in compound 1 and anhydrous THF, -78 DEG C of stirrings
N-BuLi is added dropwise in 15min~20min, is stirred to react；That borate of addition isopropanol, closes system after reaction 1.5h~2h
It is cold, reaction overnight, TLC monitorings；Stop reaction after reacting 9h~12h, water quenching is added to go out, dichloromethane extraction, dry concentration, silica gel
Column chromatography makees eluent with petrol ether/ethyl acetate, obtains pure white solid product Compound 5；
(4) synthesis of compound 6：Two-neck bottle is taken, anhydrous and oxygen-free processing sequentially adds compound 5, compound 2, four triphenylphosphines
Palladium and Anhydrous potassium carbonate under nitrogen protection, inject dry toluene and distilled water, are heated to reflux, reaction overnight, TLC monitorings；Instead
It after answering, is cooled to room temperature, dichloromethane extraction, organic phase drying concentration, silica gel column chromatography, with petrol ether/ethyl acetate
Make eluent, cross column and obtain compound 6；
(5) synthesis of compound 7：Two-neck bottle is taken, anhydrous and oxygen-free processing adds in compound 6, under nitrogen atmosphere, suck-back THF ,-
15min~20min is stirred at 78 DEG C, n-BuLi is added dropwise in syringe dropwise, continues to stir 1h~1.5h, is added dropwise with syringe super dry
DMF, the reaction was continued 5min~10min, stopping reaction；After reaction, it adds in methanol and reaction is quenched, then from -78 DEG C of environment
Lower taking-up reaction bulb, adds in a large amount of deionized waters, and after stirring evenly, reaction mixture is extracted with dichloromethane, organic relevant
It is dry, concentration, silica gel column chromatography, with petroleum ether:Dichloromethane makees eluent, obtains dark green solid product Compound 7；
(6) synthesis of acceptor material S-2：Two-neck bottle is taken, connects reflux condensing tube, anhydrous and oxygen-free processing adds in compound 7,1,1-
Methylene dicyanoethyl -3- indones, under nitrogen atmosphere, syringe injection chloroform, pyridine are heated to reflux, reaction overnight, TLC monitorings；
After reaction, stop heating, be cooled to room temperature, directly concentrate, chloroform dissolving, chloroform crosses pillar, removes unreacted indigo ketone
With the unilateral impurity in part, obtained acceptor material S-2 crude products, after S-2 crude products are dissolved in dichloromethane, in dichloromethane
Petroleum ether is gently spread on liquid level, it is overnight, it filters, the solid that petroleum ether filters out obtains pure brownish black acceptor material S-
2。
6. application of any fluorenes class organic solar batteries acceptor material of claims 1 to 3 in organic solar batteries.
7. application according to claim 6, which is characterized in that the organic solar batteries, acceptor material are right
It is required that 1~3 any fluorenes class organic solar batteries acceptor material, donor material PTB7-Th, the knot of the PTB7-Th
Structure formula is
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Application publication date: 20180608 |