CN105541694B - A series of sour cyanines small molecule in asymmetry sides and its preparation method and application - Google Patents

A series of sour cyanines small molecule in asymmetry sides and its preparation method and application Download PDF

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CN105541694B
CN105541694B CN201510897612.XA CN201510897612A CN105541694B CN 105541694 B CN105541694 B CN 105541694B CN 201510897612 A CN201510897612 A CN 201510897612A CN 105541694 B CN105541694 B CN 105541694B
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黄艳
杨琳
陈静
杨道宾
卢志云
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Sichuan University
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
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    • C07D417/10—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing aromatic rings
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Abstract

The present invention provides the sour cyanines small molecule in a series of new asymmetry side and preparation method and utilization.Using two different rich electric aromatic units as donor, by 1 with high electron affinity, 3 side's acid units, which are introduced into conjugated system, is used as receptor, forming donor-receptor-gives build asymmetry side sour cyanines small molecule, not only obtain low band gaps small molecule material, its absorption spectrum is set to cover visible and 450 800 nm of near infrared region, and this kind of compound all has good dissolubility and film forming, these are all very beneficial for the excellent organic solar batteries of processability.

Description

A series of sour cyanines small molecule in asymmetry sides and its preparation method and application
The application is the divisional application of " a series of sour cyanines small molecule in asymmetry sides and preparation method and application " application, former Shen The applying date please is on 04 03rd, 2013, and application No. is 201310114027.9, entitled " a series of asymmetry sides are sour Cyanines small molecule and preparation method and application ".
One, technical field
The present invention relates to a series of sour cyanines small molecule in asymmetry sides and preparation methods and the sour cyanines small molecule of such side to have Utilization in machine solar cell.
Two, background technology
Currently, energy crisis and environmental problem are increasingly serious, solar energy is obtained as a kind of never exhausted clean energy resource Everybody attention.It is aobvious that organic solar batteries (OPV) compared with inorganic solar cell have that at low cost, light-weight, flexibility is good etc. Write advantage.In recent years, compared to polymer solar battery, small molecule organic solar batteries are due to determining molecule knot Structure, the molecular mass of determination and the advantages that be easily purified, thus have received widespread attention and study.For promote it practical into Journey, research and development more visible and near infrared region have strong absorption, be easy the micromolecular compound donor material prepared for The efficiency for improving photovoltaic device is of great significance.
Squarylium cyanine dyes are because of its excellent photochemistry and optical physics stability, and in the strong of visible and near-infrared region It absorbs, the application in organic solar batteries field gradually causes the interest of people.2008, Pag ani et al first Secondary to report the symmetric form side's acid cyanines small molecule organic solar batteries processed based on solution, electricity conversion (PCE) is 1.24% (J.Am.Chem.Soc.2008,130,17640-17641.).Up to now, symmetric form side's acid based on solution processing The PCE of the body heterojunction organic solar batteries of cyanines small molecule up to 5.50% (Adv.Energy.Mater.2011,1, 184-187.), at the same the PCE of its double-deck organic solar batteries be up to 6.30% (Nano Lett.2011,11,4261- 4264.), the sour cyanines material in the side of showing is rich in application prospect in this field.Compared with the symmetric form sides the 1,3- acid cyanines of current function admirable The performance of photovoltaic material, asymmetry side's acid cyanines is relatively low, and applicant only retrieves the sour cyanine compound in four asymmetry sides in OPV In application (Angew.Chem., Int.Ed.2009,48,8776-8779；Sol.Energy Mater.S ol.Cells 2012,98,224-232；ACS Nano 2012,6,972-978；J.Mater.Chem. 2012,22,6704-6710), ACS The material property reported in Nano is best, but optical energy gap is about in 2. 0eV, relatively high, bad with the matching of solar spectrum.
Side's acid cyanine compound is formed with electron rich aromatic ring or heterocyclic condensation by side's acid, and can forming 1,3- substitutions, (structure is shown In figure below), it is identical or differ according to X, Y, it is divided into be symmetrical with asymmetric two types.In general, asymmetry side's acid cyanines With better dissolubility, it is most important that there is more rich adjustability of structure, in dye-sensitized solar cells, electrostatic It duplicates, near-infrared increases the photosensitive application aspects such as sense with compared with the more excellent performance of symmetric form side's acid compound.Thus design, conjunction At the sour cyanines photovoltaic material in novel asymmetry side, it is of great significance to building new and effective photovoltaic material.
Three, invention content
One of the objects of the present invention is to provide the sour cyanines small molecules in a series of new asymmetry side.
The present invention provides the asymmetry side with following general formula I sour cyanines small molecule, and A, B represent the electric aromatic rings list of different richnesses Member,
Its structure feature is：
The A is following group 1：
Group 1：
The B is any one in following group 2, group 3, group 4,
Group 2：
Group 3：
Group 4：
The second object of the present invention is to provide the preparation method of the sour cyanines small molecule in any asymmetry side of the present invention, It is characterized in that step and reaction condition are：Under high-purity argon gas protection, two reaction substrates of equimolar amounts proportioning are sequentially added, With toluene:The volume ratio of n-butanol is 1:1 mixed solution divides water back flow reaction 13h, reaction to finish as solvent, heating, steams Solvent is sent out to dry, obtained residue is subjected to column chromatography for separation, collects respective components, recrystallization, synthetic route is as follows：
Wherein, Ar is the compound corresponding to group 2 described in claim 1, group 3, group 4, and structure is：
Compound 2：
Compound 3：
Compound 4：
The third object of the present invention is to provide the purposes of acid cyanines small molecule in asymmetry side's in the present invention, especially organic Utilization on solar cell.
The organic solar batteries device architecture as shown in figure 5, a be body heterojunction device architecture, wherein M oO3Thickness Degree is 6-10nm or PEDOT:The thickness of PSS is 30-40nm；The blend film of asymmetry side's acid cyanines small molecule and PCBM are lived for light Property layer, thickness 20-400nm；The thickness of LiF is 0.5-0.8 nm；The thickness of Al or Ag electrodes is 60-200nm.B is bilayer Device architecture, wherein MoO3Thickness be 6-16nm or PEDOT:The thickness of PSS is 30-40nm；Asymmetry side's acid cyanines small molecule As the p-type semiconductor material of photoactive layer, film thickness 4-80nm；C60Or C70N type semiconductors as photoactive layer The degree of material, film is 20-80nm；The thickness of BCP (chemical constitution is shown in figure) is 5-20 nm；The thickness of Al or Ag electrodes For 60-200nm.
Advantageous effect：The sour cyanines small molecule material in asymmetry side provided by the invention, the light for being used as organic solar batteries are lived Property layer, advantage are：
(1) there is good dissolubility.Relative to classical symmetric form side's acid cyanines small molecule photovoltaic material SQ (chemical structural formulas It is as follows) for, the sour cyanines small molecule material in asymmetry side provided by the invention common organic solvents (such as：Chloroform, tetrahydrofuran, Chlorobenzene, o-dichlorohenzene etc.) in there is better dissolubility (dissolubility data be listed in table 1, and 6a is that asymmetry side is sour in embodiment 1 Cyanines small molecule), while also there is good film forming, these are all very beneficial for the solution processing processability using low cost Excellent organic solar batteries.
Table 1：The solubility data (mg/mL) (15 DEG C) of side's acid cyanines small molecule
Solvent N-hexane Toluene Chloroform Chlorobenzene O-dichlorohenzene Acetone Tetrahydrofuran Methanol
SQ a <1 <6 <2 <2 <1 <0.7 a
6a <0.1 >30 >90 >90 >90 >50 >20 <0.1
Note：A indicates insoluble
(2) there is broader absorption spectrum.Relative to the asymmetry side's acid reported in ACS Nano 2012,6,972-978. The spectral response range of cyanines small molecule, the sour cyanines small molecule material in asymmetry side provided by the invention is wider (450-800nm), with Solar spectrum more matches, this is beneficial to improve the absorption to sunlight, improves the electricity conversion of photovoltaic device.
The sour small molecule in the asymmetry side of preparation is that the organic solar batteries device performance of donor material is respectively：White light 1.5G(100mw/cm2) under irradiation, open-circuit voltage (Voc)=0.70-1.20V, short circuit current (Js c)=4.76-12.10mA/ cm2, fill factor (FF)=0.30-0.70, electricity conversion (PCE)=1. 03-5.05%.
Four, it illustrates
Fig. 1 is that asymmetry side acid 6a is in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film in embodiment 1, together When be also Figure of abstract.
Fig. 2 be in embodiment 3 asymmetry side acid 6c in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film.
Fig. 3 is the organic sun of body heterojunction of asymmetry side acid 6e in asymmetry side acid 6a and embodiment 5 in embodiment 1 The current -voltage curve of energy battery device.
Fig. 4 is the organic sun of body heterojunction of asymmetry side acid 6e in asymmetry side acid 6a and embodiment 5 in embodiment 1 The external quantum efficiency figure of energy battery device.
Fig. 5 is the structural schematic diagram of organic solar batteries device.
Five, specific implementation mode
Embodiment 1：The preparation of asymmetry side acid 6a
(1) 3- ((3- butyl -1,1- dimethyl -1H benzos [e] indoles -2 (3H)-subunit) methyl) -4- ethoxy basic ring butyl- The preparation of 3- alkene -1,2- diketone 3a
2a 5.00g (12.7mmol) (synthetic method is shown in Eur.J.Org.Chem.2008,12,2107-211 7.) are added 120mL mixed solvent (triethylamines:Ethyl alcohol=1:8, v/v), it is heated to reflux 30min.It is cooled to room temperature, 1 1.83g is added (12.7mmol) (synthetic method is shown in J.Am.Chem.Soc.2007,129,10 320-10321.), back flow reaction 30min, decompression Steam solvent, column chromatography (PE:EA=8:1), ethyl alcohol recrystallization obtains orange-yellow crystal 2.04g, yield 68%.m.p.187-188 ℃；1H NMR(CDCl3,400M Hz,ppm)δ:8.11 (d, J=8.4Hz, 1H), 7.89 (d, J=8.4Hz, 1H), 7.85 (d, J =8.4Hz, 1H), 7.54 (t, J=7.6Hz, 1H), 7.38 (t, J=7.6Hz, 1H), 7.23 (d, J=8. 8Hz, 1H), 5.46 (s, 1H), 4.96 (q, J=7.2Hz, 2H), 3.94 (t, J=7.2Hz, 2H), 1.9 0 (s, 6H), 1.83-1.75 (m, 2H), 1.58 (t, J=7.2Hz, 3H), 1.50-1.43 (m, 2H), 1.0 1 (t, J=7.2Hz, 3H).
(2) 3- ((3- butyl -1,1- dimethyl -1H- benzos [e] indoles -2 (3H)-subunit) methyl) -4- hydroxyl ring butyl- The preparation of 3- alkene -1,2- diketone 4a
40mL absolute ethyl alcohols are added in 3a 2.04g (5.2mmol), and 3mL 40%NaO H, reaction are added under reflux state 30min, decompression rotation remove solvent, and residue is dissolved in 20mL water, and saturated lemon is added dropwise to PH=3~4, and yellow mercury oxide is precipitated, Filter to obtain yellow powder 1.32g, yield 70%.1H NMR(DMSO-d6, 400MHz,ppm)δ:8.06 (d, J=8.8Hz, 1H), 7.85 (d, J=8.0Hz, 1H), 7.81 (d, J=8.8Hz, 1H), 7.45 (t, J=7.6Hz, 1H), 7.34 (d, J=8.8Hz, 1H), 7.2 3 (t, J=7.6Hz, 1H), 5.45 (s, 1H), 3.83 (t, J=7.2Hz, 2H), 1.83 (s, 6H), 1. 68-1.61 (m, 2H), 1.43-1.34 (m, 2H), 0.93 (t, J=7.6Hz, 3H).
(3) preparation of 5- (di-iso-butylmanice) benzene -1,3- diphenol 5a
Under argon gas protection, phloroglucin 10.00g (79.3mmol), di-iso-butylmanice 20.50g (158.6mmol) are added 280mL mixed solvent (n-butanols:Toluene=1:3) in, water reflux 6h, decompression is divided to steam solvent, column chromatography (petroleum ether：Acetone =4:1) brown-red solid, yield 24% are obtained.1H NMR(CDCl3,400M Hz,ppm)δ:10.96(s,2H),5.80(s,2H), 5.64 (s, 1H), 3.24 (d, J=7.4Hz, 4 H), 2.12 (m, 2H), 0.92 (d, J=6.6Hz, 12H).
(4) preparation of asymmetry side's acid 6a
4a 0.6250g (1.7mmol), 5a 0.4035g (1.7mmol), 80mL mixed solvent (toluene:N-butanol=1: 1, v/v) water reflux 13h, decompression, is divided to steam solvent, column chromatography (CH2Cl2:CH3OH=50:1) (dichloromethane/first, is recrystallized Alcohol) obtain bright yellow solid 0.80g, yield 23%.M.p.198-199 DEG C,1H NMR(CDCl3,400MHz,ppm)δ:12.41(s, 2H), 8.20 (d, J=8.5Hz, 1H), 7.91 (dd, J=7.7,8.4Hz, 2H), 7.59 (t, J=7.4Hz, 1H), 7.46 (t, J=7.7Hz, 1H), 7.32 (d, J=8.8Hz, 1H), 5.85 (s, 1H), 5.80 (s, 2H), 4.13 (t, J=7.4Hz, 2H), 3.22 (d, J=7.4Hz, 4H), 2.20-2.10 (m, 2H), 2.01 (s, 6H), 1.88-1.81 (m, 2H), 1. 54-1.44 (m, 2H), 1.01 (t, J=7.3Hz, 3H), 0.92 (d, J=6.8Hz, 12H).
Embodiment 2：The preparation of asymmetry side acid 6b
(1) preparation of compound 4a is the same as embodiment 1.
(2) preparation of asymmetry side's acid 6b
(synthetic method is shown in Dyes and Pigments. by 4a 1.00g (2.8mmol), 5b 0.68g (2.8mmol) 2003.59,63-69.), 80mL mixed solvents (toluene:N-butanol=1:1, v/v) water 13 h of reflux, decompression, is divided to steam solvent, Column chromatography (CH2Cl2:CH3OH=50:1), recrystallization (methylene chloride/methanol) obtains bright green crystal 6b 0.88g, yield 54%.1H NMR(CDCl3,400MHz,ppm)δ:12.4 8 (s, 2H), 8.19 (d, J=8.4Hz, 1H), 8.04 (s, 1H), 7.92 (dd, J=9.2,9.2Hz, 2 H), 7.60 (t, J=7.6Hz, 1H), 7.45 (t, J=7.2Hz, 1H), 7.32 (d, J= 8.8Hz, 1H),5.98(s,1H),4.13(s,2H),3.30(br,4H),2.04(s,6H),1.88-1.81(m,2H), 1.77-1.71 (m, 4H), 1.54-1.45 (m, 2H), 1.48 (s, 6H), 1.31 (s, 6H), 1.02 (t, J=7.2Hz, 3H).
Embodiment 3：The preparation of asymmetry side acid 6c
(1) preparation of compound 4a is the same as embodiment 1.
(2) preparation of 5-9H- carbazoles -9- phenyl -1,3- glycol 5c
Carbazole 5.00g (30mmol), 3,5- dimethoxy bromobenzene 7.80g (36mmol), the Pd (O Ac) of 3% mole2, The P (t-Bu) of 6% mole3.BF4, the sodium tert-butoxide of 1.5 times of moles is added in 200mL toluene, 1 10 DEG C of heating 12h, mistake Filter, filtrate decompression rotation remove solvent, column chromatography (PE:EA), petroleum ether recrystallizes to obtain white needle-like crystals 9- (3,5- dimethoxys- Phenyl) -9H- carbazole 6.60g, yield 73%.1H NMR(C DCl3,400MHz,ppm)δ:8.13 (d, J=8.0Hz, 2H), 7.48 (d, J=7.6Hz, 2 H), 7.41 (t, J=7.6Hz, 2H), 7.29 (t, J=7.6Hz, 2H), 6.72 (s, 2H), 6.56 (s, 1H),3.84(s,6H)。
40mL anhydrous methylene chlorides, ice bath is added in 9- (3,5- dimethoxy-phenylf) -9H- carbazoles 1.00g (3.30mmol) Under the anhydrous methylene chloride solution of 34mL 8.26g containing Boron tribromide (33.00mmol) is slowly added dropwise, after being added dropwise, rise naturally It warms to room temperature, stirs 36h.Reaction solution is poured into 150mL ice water, is extracted with dichloromethane, water washing, saturated sodium carbonate washing, Dry, concentration, column chromatography obtains 0.8 0g of white powder, yield 88%.1H NMR(CDCl3,400MHz,ppm)δ：8.12 (d, J= 8.0Hz, 2 H), 7.49 (t, J=7.6Hz, 2H), 7.40 (t, J=8.0Hz, 2H), 7.25 (t, J=7.6Hz, 2H), 6.63 (s,2H),6.44(s,1H)。
(3) preparation of asymmetry side's acid 6c
4a 1.00g (2.8mmol), 5c 0.77g (2.8mmol), 80mL mixed solvent (toluene:N-butanol=1:1, v/ V), water reflux 13h, decompression is divided to steam solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride/methanol) obtains glassy yellow Crystal 0.35g, yield 20%.1H NMR(DMSO-d6,400MHz, ppm)δ:12.20 (s, 2H), 8.44 (d, J=8.4Hz, 1H), 8.24 (d, J=7.6Hz, 2H), 8. 23 (d, J=9.2Hz, 1H), 8.17 (d, J=8.0Hz, 1H), 8.08 (d, J= 9.4Hz,1H), 7.78-7.73(m,3J=7.2Hz,4J=0.8Hz, 1H), 7.68 (t, J=7.2Hz, 1H), 7.60 (d, J= 8.4Hz,2H),7.51-7.46(m,3J=7.2Hz,4J=0.8Hz, 2H), 7.34-7.30 (m,3J=7.2Hz,4J= 0.4Hz, 2H), 6.55 (s, 2H), 6.42 (s, 1H), 4.66 (t, J=7.2 Hz, 2H), 2.02 (s, 6H), 1.91-1.83 (m, 2H), 1.52-1.43 (m, 2H), 0.97 (t, J=7.2Hz, 3H).
Embodiment 4：The preparation of asymmetry side acid 6d
(1) preparation of compound 1 is the same as embodiment 1.
(2) 3- ethyoxyls -4- ((3- ethyls naphtho- [2,1-d] thiazole -2 (3H)-subunit) methyl) ring butyl- 3- alkene -1,2- The preparation of diketone 3b
It is mixed that 20mL is added in 2b 2.52g (7.06mmol) (synthetic method is shown in J.Org.Chem.1995,60,2391-2395.) Bonding solvent (triethylamine:Ethyl alcohol=1:8, v/v), it is heated to reflux 30min.1 1.20g (7. 06mmol), back flow reaction is added dropwise 15min, decompression steam solvent, column chromatography (PE:EA=8:1), ethyl alcohol recrystallization obtains orange-yellow crystal 1.98g, yield 80%.1H NMR(CDCl3,400MHz,ppm)δ:8.17 (d, J=8.4Hz, 1H), 7.90 (d, J=8.4Hz, 1H), 7.85 (d, J= 8.4Hz, 1H), 7.76 (t, J=7.6Hz, 1H), 7.43 (t, J=7.6Hz, 1H), 7.29 (d, J=8.8Hz, 1H), 5.38 (s,1
), H 4.96 (q, J=7.2Hz, 2H), 3.83 (q, J=7.2Hz, 2H), 1.49 (t, J=7.2Hz, 3 H), 1.93 (t, J=7.2Hz, 3H).
(3) 3- ((3- ethyls naphtho- [2,1-d] thiazole -2 (3H)-subunit) methyl) -4- hydroxyl ring butyl- 3- alkene -1,2- two The preparation of ketone 4b
40mL absolute ethyl alcohols are added in 3b 1.84g (5.24mmol), and 3mL 40%Na OH, reaction are added under reflux state 30min, decompression rotation remove solvent, and residue is dissolved in 20mL water, and saturated lemon is added dropwise to PH=3~4, and yellow mercury oxide is precipitated, Filter to obtain yellow powder 1.02g, yield 60%.1H NMR(DMSO- d6,400MHz,ppm)δ:8.21 (d, J=8.8Hz, 1H), 8.01 (d, J=8.4Hz, 1H), 7.7 9 (d, J=8.4Hz, 1H), 7.45 (t, J=7.6Hz, 1H), 7.25 (d, J=8.8Hz, 1H), 7. 14 (t, J=7.6Hz, 1H), 5.38 (s, 1H), 4.57 (q, J=7.2Hz, 2H), 1.84 (t, J=7.2Hz, 3H).
(4) preparation of compound 5a is the same as embodiment 1.
(5) preparation of asymmetry side's acid 6d
4b 0.5694g (1.73mmol), 5a 0.4106g (1.73mmol), 80mL mixed solvent (toluene:N-butanol= 1:1, v/v) water reflux 13h, decompression, is divided to steam solvent, column chromatography (CH2Cl2:CH3OH), recrystallization (methylene chloride/methanol) obtains There are metallic luster solid 0.32g, yield 34%.1H NMR(CDCl 3,400MHz,ppm)δ:12.20 (s, 2H), 8.21 (d, J= 8.8Hz, 1H), 7.91 (dd, J=7.6,8.4Hz, 2H), 7.64 (t, J=7.4Hz, 1H), 7.46 (t, J=7.6Hz, 1H), 7.23 (d, J=8. 8Hz, 1H), 5.79 (s, 1H), 5.72 (s, 2H), 4.13 (q, J=7.2Hz, 2H), 3.22 (d, J=7. 2Hz, 4H), 2.21-2.13 (m, 2H), 1.90 (t, J=7.6Hz, 3H), 0.92 (d, J=6.8Hz, 12H).
Embodiment 5：The preparation of asymmetry side acid 6e
(1) preparation of compound 4b is the same as embodiment 4.
(2) preparation of compound 5b is the same as embodiment 2.
(3) preparation of asymmetry side's acid 6e
4b 0.9054 (2.8mmol), 5b 0.6870g (2.8mmol), 80mL mixed solvent (toluene:N-butanol=1:1, V/v), water reflux 13h, decompression is divided to steam solvent, column chromatography (CH2Cl2:CH3OH=50:1), (methylene chloride/methanol) is recrystallized Obtain bright yellow solid 0.74g, yield 48%.1H NMR(CDCl3,4 00MHz,ppm)δ:12.27 (s, 2H), 8.19 (d, J= 8.4Hz, 1H), 7.90 (s, 1H), 7.83 (dd, J=9.2,9.2Hz, 2H), 7.75 (t, J=7.6Hz, 1H), 7.54 (t, J= 7.2Hz, 1H), 7.30 (d, J=8.8Hz, 1H), 5.45 (s, 1H), 4.57 (q, J=7.2Hz, 2H), 3.30 (br, 4 H), 2.04 (t, J=7.2Hz, 3H), 1.79-1.70 (m, 4H), 1.37 (s, 6H), 1.28 (s, 6H).
Embodiment 6：The preparation of asymmetry side acid 6f
(1) preparation of compound 4b is the same as embodiment 4.
(2) preparation of compound 5c is the same as embodiment 3.
(3) preparation of asymmetry side's acid 6f
4b 0.9054g (2.8mmol), 5c 0.7708g (2.8mmol), 80mL mixed solvent (toluene:N-butanol=1: 1, v/v) water reflux 13h, decompression, is divided to steam solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride/methanol) obtains green Color crystal 0.44g, yield 27%.1H NMR(DMSO-d6,400 MHz,ppm)δ:12.20 (s, 2H), 8.34 (d, J=8.4Hz, 1H), 8.14 (d, J=7.6Hz, 2H), 8.05 (d, J=8.8Hz, 1H), 7.99 (d, J=8.0Hz, 1H), 7.91 (d, J= 9.4H z, 1H), 7.87 (t, J=7.6Hz, 1H), 7.68 (t, J=7.2Hz, 1H), 7.63 (d, J=8.4 Hz, 2H), 7.51 (t, J=7.2Hz, 2H), 7.34-7.30 (t, J=7.2Hz, 2H), 6.68 (s, 2H), 6.35 (s, 1H), 4.54 (q, J= 7.2Hz, 2H), 1.91 (t, J=7.2Hz, 3H).
Embodiment 7：The preparation of asymmetry side's acid 6a organic solar batteries devices
(1) device architecture 3mg 6a as shown in Figure 5 a are mixed with 17mg PCBM, the dissolving of 1mL chloroforms are added, by spin coating side Formula is through MoO3Film is prepared on the ito glass substrate of modified, then vacuum evaporation LiF and Al prepare cathode.White light 1.5G(100mW/cm2) under irradiation, device photoelectric transformation efficiency (PCE) is 2.24%.
(2) the 6a chloroformic solutions of device architecture 1mg/mL as shown in Figure 5 b are spin-coated on through MoO3The ito glass base of modified On plate, then vacuum evaporation C successively60Layer, BCP layers and Al electrode layers.1.5 G (100mW/cm of white light2) under irradiation, device photoelectric Transformation efficiency (PCE) is 4.23%.
Embodiment 8：The preparation of asymmetry side's acid 6c organic solar batteries devices
(1) device architecture 3mg 6c as shown in Figure 5 a are mixed with 17mg PCBM, the dissolving of 1mL chloroforms are added, by spin coating side Formula is through MoO3Film is prepared on the ito glass substrate of modified, then vacuum evaporation LiF and Al prepare cathode.White light 1.5G(100mW/cm2) under irradiation, device open-circuit voltage (Voc)=1.09V, electricity conversion (PCE) is 2.20%.
(2) device architecture is as shown in Figure 5 b through MoO3Vacuum evaporation 6c films successively on the ito glass substrate of modified Layer, C60Layer, BCP layers and Al electrode layers.White light 1.5G (100mW/cm2) under irradiation, device photoelectric transformation efficiency (PCE) is 4.58%.
Embodiment 9：The preparation of asymmetry side's acid 6e organic solar batteries devices
(1) device architecture 4mg 6e as shown in Figure 5 a are mixed with 16mg PCBM, the dissolving of 1mL chloroforms are added, by spin coating side Formula is through MoO3Film is prepared on the ito glass substrate of modified, then vacuum evaporation LiF and Al prepare cathode.White light 1.5G(100mW/cm2) under irradiation, device photoelectric transformation efficiency (PCE)=1.72%.
(2) the 6e chloroformic solutions of device architecture 1mg/mL as shown in Figure 5 b are spin-coated on through MoO3The ito glass base of modified On plate, then vacuum evaporation C successively60Layer, BCP layers and Al electrode layers.1.5 G (100mW/cm of white light2) under irradiation, device photoelectric Transformation efficiency (PCE) is 3.97%.
Table 2：The device photoelectric transformation efficiency PCE (%) of side acid cyanines small molecule 6a-6f
Side's acid cyanines small molecule 6a 6b 6c 6d 6e 6f
Bulk heteroj junction device 2.24 2.08 2.20 2.59 1.72 2.93
Bi-layer devices 4.23 3.40 4.58 3.15 3.97 4.07

Claims (3)

  1. It is 1. a series of that there is the sour cyanines small molecule in the asymmetry side of logical structure shown in formula I, A, B to represent the different fragrant ring elements of rich electricity,
    Its structure feature is：
    The A is following group 1：
    Group 1：
    The B is any one in following group 2, group 3, group 4,
    Group 2：
    Group 3：
    Group 4：
  2. 2. the preparation method of the sour cyanines small molecule in any asymmetry side as described in claim 1, it is characterised in that step and reaction item Part is：Under high-purity argon gas protection, two reaction substrates of equimolar amounts proportioning are sequentially added, with toluene:The volume of n-butanol Than being 1:1 mixed solution divides water back flow reaction 13h, reaction to finish as solvent, heating, and evaporation solvent is to doing, by what is obtained Residue progress column chromatography for separation, collection respective components, recrystallization, synthetic route are as follows：
    Wherein, Ar is the compound corresponding to group 2 described in claim 1, group 3, group 4, and structure is：
    Compound 2：
    Compound 3：
    Compound 4：
  3. 3. application of the sour cyanines small molecule in any asymmetry side in organic solar batteries as described in claim 1.
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