CN103214410A - Series of asymmetrical squarine micromolecules as well as preparation method and application thereof - Google Patents

Series of asymmetrical squarine micromolecules as well as preparation method and application thereof Download PDF

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CN103214410A
CN103214410A CN2013101140279A CN201310114027A CN103214410A CN 103214410 A CN103214410 A CN 103214410A CN 2013101140279 A CN2013101140279 A CN 2013101140279A CN 201310114027 A CN201310114027 A CN 201310114027A CN 103214410 A CN103214410 A CN 103214410A
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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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Abstract

The invention discloses a series of asymmetrical squarine micromolecules as well as a preparation method and an application thereof. Donor-receptor-donor type asymmetrical squarine micromolecules are formed by adopting two different electron-rich aromatic units as donors and leading 1,3-squaric acid cells with high electronic affinity into a conjugated system as receptors, so that micromolecule materials with low band gaps are acquired, and the absorption spectrum of the micromolecule materials can cover visual and near-infrared regions by 450-800nm; and meanwhile, the compounds prepared through the preparation method are good in dissolubility and film-forming property, which is very favorable for preparing organic solar cells with good performance.

Description

Sour cyanines small molecules of a series of asymmetric sides and its production and application
One, technical field
The present invention relates to sour cyanines small molecules of a series of asymmetric sides and preparation method, and the utilization of the sour cyanines small molecules of such side in organic solar batteries.
Two, background technology
At present, energy dilemma and environmental problem are increasingly serious, and sun power has obtained everybody attention as a kind of never exhausted clean energy.Organic solar batteries (OPV) has remarkable advantages such as cost is low, in light weight, snappiness is good than inorganic solar cell.In recent years, compared to polymer solar battery, the small molecules organic solar batteries is owing to have definite molecular structure, definite molecular mass and easy advantage such as purification, thereby has been subjected to paying close attention to widely and studying.For advancing its practicalization, it is significant for the efficient that improves photovoltaic device to research and develop more micromolecular compound donor materials that in visible and near-infrared region strong absorption arranged, prepare easily.
Indolenium squaraine cyanine dye is because of its good photochemistry and optical physics stability, and in the strong absorption of visible and near-infrared region, caused people's interest gradually in the application in organic solar batteries field.2008, Pagani et al reported the symmetric form side's acid cyanines small molecules organic solar batteries based on solution processing for the first time, and its electricity conversion (PCE) is 1.24%(J. Am. Chem. Soc. 2008,130,17640-17641.).Up to now, PCE based on the micromolecular body heterojunction organic solar batteries of symmetric form side's acid cyanines of solution processing has reached 5.50%(Adv. Energy. Mater. 2011,1,184-187.), the PCE of its double-deck organic solar batteries is up to 6.30%(Nano Lett. 2011 simultaneously, 11,4261-4264.), the sour cyanines material in the side of showing is rich in application prospect in this field.Than 1 of present excellent property, 3-symmetric form side acid cyanines photovoltaic material, the performance of the sour cyanines of asymmetric side is low relatively, the applicant only retrieves application (the Angew. Chem. of four pieces of sour cyanine compounds of asymmetric side in OPV, Int. Ed. 2009,48, and 8776-8779; Sol. Energy Mater. Sol. Cells 2012,98,224-232; ACS Nano 2012,6,972-978; J. Mater. Chem. 2012,22,6704-6710), and material property the best of reporting among the ACS Nano, but optical energy gap is higher relatively about 2.0 eV, and not good with the coupling of solar spectrum.
Square sour cyanine compound is to be formed by side's acid and electron rich aromatic ring or heterocycle condensation, can form 1, and 3-replaces (structure is shown in figure below), and is identical or inequality according to X, Y, is divided into symmetrical again and asymmetric two types.Generally speaking, the sour cyanines of asymmetric side have better solvability, the most important thing is to have more abundant structures adjustability, have the performance more excellent than symmetric form side's acid compound in photosensitive application facet such as dye-sensitized solar cells, xerox, near infrared sensitizing.Thereby design, the sour cyanines photovoltaic material of the asymmetric side of synthesizing new, significant to making up new and effective photovoltaic material.
Figure GDA0000300756211
Three, summary of the invention
One of purpose of the present invention is to provide a series of novel asymmetric sides sour cyanines small molecules.
The invention provides the sour cyanines small molecules of the asymmetric side with following formula I, the rich electric aromatic nucleus unit that A, B representative is different,
Figure GDA0000300756212
Its constitutional features is:
Described A is any one in following group 1 or 2, wherein R 1The alkoxyl group or the carbonatoms that for hydrogen atom or fluorine atom or cyano group or phenyl or phenoxy group or carbonatoms are the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or the carbonatoms straight or branched that is 1-20 are the alkoxyphenyl radical of the straight or branched of 1-20, R 2Be that the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for carbonatoms.
Group 1:
Figure GDA0000300756213
Group 2:
Figure GDA0000300756214
Described B is any one in the following group 3 to 5,
Group 3:
In the group 3, R 1And R 2Be hydroxyl or R 1Be hydroxyl and R 2Be hydrogen atom, R 3And R 4Be that the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for carbonatoms identical or inequality.
Group 4:
Figure GDA0000300756216
In the group 4, R 1And R 2Be hydrogen atom identical or inequality or hydroxyl, R 3, R 4, R 5And R 6For hydrogen atom identical or inequality or carbonatoms are the alkyl of the straight or branched of 1-20.
Group 5:
Figure GDA0000300756217
In the group 5, R 1And R 2Be hydrogen atom identical or inequality or hydroxyl, R 3, R 4, R 5And R 6Be that the alkoxyl group of the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or the carbonatoms straight or branched that is 1-20 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for hydrogen atom identical or inequality or carbonatoms.
Two of purpose of the present invention is to provide the sour cyanines of arbitrary asymmetric side of the present invention micromolecular preparation method; it is characterized in that step and reaction conditions are: under the high-purity argon gas protection; two reaction substrates that add the equimolar amount proportioning successively; with toluene: mixing solutions propyl carbinol=1:1(volume ratio) is as solvent; heating divides the water back flow reaction 13 h; reaction finishes; evaporating solvent is to doing; the resistates that obtains is carried out column chromatography for separation; collect respective components; recrystallization gets final product, and synthetic route is as follows:
Figure GDA0000300756218
Figure GDA0000300756219
Wherein, Ar is the pairing compound of group 3-5 described in the claim 1, and its structure is:
Compound 3:
Figure GDA00003007562110
Compound 4:
Figure GDA00003007562111
Compound 5:
Figure GDA00003007562112
Three of purpose of the present invention is to provide the sour cyanines of asymmetric side micromolecular purposes, the particularly utilization on organic solar batteries among the present invention.
This organic solar batteries device architecture as shown in Figure 5, a is body heterojunction device architecture, wherein MoO 3Thickness be that the thickness of 6-10 nm or PEDOT:PSS is 30-40 nm; The blend film of sour cyanines small molecules of asymmetric side and PCBM is a photoactive layer, and thickness is 20-400 nm; The thickness of LiF is 0.5-0.8 nm; The thickness of Al or Ag electrode is 60-200 nm.B is bi-layer devices structure, wherein MoO 3Thickness be that the thickness of 6-16 nm or PEDOT:PSS is 30-40 nm; The sour cyanines small molecules of asymmetric side is as the P-type semiconductor material of photoactive layer, and film thickness is 4-80 nm; C 60Or C 70As the N-type semiconductor material of photoactive layer, the degree of film is 20-80 nm; The thickness of BCP (chemical structure is shown among the figure) is 5-20 nm; The thickness of Al or Ag electrode is 60-200 nm.
Beneficial effect: the sour cyanines small molecule material of asymmetric side provided by the invention, as the photoactive layer of organic solar batteries, its beneficial effect is:
(1) good solubility is arranged.Symmetric form side's acid cyanines small molecules photovoltaic material SQ(chemical structural formula with respect to classics is as follows) for, the sour cyanines small molecule material of asymmetric side provided by the invention is at common organic solvent (as: chloroform, tetrahydrofuran (THF), chlorobenzene, orthodichlorobenzenes etc.) (dissolubility data is listed in table 1 to have better solvability in, 6a is the sour cyanines small molecules of asymmetric side among the embodiment 1), simultaneously also have good film-forming properties, these all are very beneficial for adopting the organic solar batteries of solution processing and preparing excellent property cheaply.
Figure GDA00003007562113
Table 1: side's micromolecular solubility data of sour cyanines (mg/mL) (15 ℃)
Solvent Normal hexane Toluene Trichloromethane Chlorobenzene Orthodichlorobenzene Acetone Tetrahydrofuran (THF) Methyl alcohol
SQ --- a < 1 < 6 < 2 < 2 < 1 < 0.7 --- a
6a < 0.1 > 30 > 90 > 90 > 90 > 50 > 20 < 0.1
Annotate: a represents insoluble
(2) wideer absorption spectrum is arranged.With respect to ACS Nano 2012,6,972-978. the sour cyanines small molecules of the asymmetric side of middle report, the film spectral response range of the sour cyanines small molecule material of asymmetric side provided by the invention wideer (450-800 nm), more mate with solar spectrum, this will help improving the absorption to sunlight, improve the electricity conversion of photovoltaic device.
The sour small molecules of asymmetric side of preparation is that the organic solar batteries device performance of donor material is respectively: white light 1.5 G(100 mw/cm 2) shine down open circuit voltage (Voc)=0.70-1.20V, short-circuit current (Jsc)=4.76-12.10 mA/cm 2, packing factor (FF)=0.30-0.70, electricity conversion (PCE)=1.03-5.05%.
Four, description of drawings
Fig. 1 is that the sour 6a of asymmetric side also is a Figure of abstract simultaneously in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film among the embodiment 1.
Fig. 2 be among the embodiment 3 the sour 6c of asymmetric side in chloroformic solution and the ultraviolet-visible absorption spectroscopy of solid film.
Fig. 3 is the current-voltage curve of the body heterojunction organic solar batteries device of the sour 6e of asymmetric side among the sour 6a of asymmetric side and the embodiment 5 among the embodiment 1.
Fig. 4 is the external quantum efficiency figure of the body heterojunction organic solar batteries device of the sour 6e of asymmetric side among the sour 6a of asymmetric side and the embodiment 5 among the embodiment 1.
Fig. 5 is the structural representation of organic solar batteries device.
Five, embodiment
Embodiment 1: the preparation of the sour 6a of asymmetric side
(1) 3-((3-butyl-1,1-dimethyl-1H benzo [e] indoles-2 (3H)-subunit) methyl)-4-ethoxy basic ring fourth-3-alkene-1, the preparation of 2-diketone 3a
2a 5.00g (12.7mmol) (synthetic method is seen Eur. J. Org. Chem. 2008,12,2107 – 2117.) adding 120mL mixed solvent (triethylamine: ethanol=1:8, v/v), reflux 30min.Be cooled to room temperature, (synthetic method is seen J. Am. Chem. Soc. 2007,129 to add 1 1.83g (12.7mmol), 10320-10321.), back flow reaction 30min, decompression steams solvent, column chromatography (PE:EA=8:1), ethyl alcohol recrystallization get orange-yellow crystal 2 .04g, productive rate 68%.m.p. 187-188℃; 1H NMR (CDCl 3, 400MHz, 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), 1.90 (s, 6H), 1.83-1.75 (m, 2H), 1.58 (t, J = 7.2Hz, 3H), 1.50-1.43 (m, 2H), 1.01 (t, J = 7.2Hz, 3H)。
(2) 3-((3-butyl-1,1-dimethyl-1H-benzo [e] indoles-2 (3H)-subunit) methyl)-4-hydroxyl ring fourth-3-alkene-1, the preparation of 2-diketone 4a
3a 2.04g (5.2mmol) adds the 40mL dehydrated alcohol, and reflux state adds 3mL 40% NaOH, reaction 30min down, decompression is revolved and is desolventized, and resistates is dissolved in 20mL water, drips saturated citric acid to PH=3 ~ 4, yellow mercury oxide is separated out, filter yellow powder 1.32g, productive rate 70%. 1H NMR (DMSO-d 6, 400MHz, ppm)δ: 8.06 (d, J = 8.8 Hz, 1H), 7.85 (d, J = 8.0 Hz, 1H), 7.81 (d, J = 8.8 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.34 (d, J = 8.8 Hz, 1H), 7.23 (t, J = 7.6 Hz, 1H), 5.45 (s, 1H), 3.83 (t, J = 7.2 Hz, 2H), 1.83 (s, 6H), 1.68-1.61 (m, 2H), 1.43-1.34(m, 2H), 0.93 (t, J = 7.6 Hz, 3H)。
(3) benzene-1 5-(diisobutylamine), the preparation of 3-diphenol 5a
Under the argon shield, Phloroglucinol 10.00g (79.3mmol), diisobutylamine 20.50g (158.6mmol) add 280mL mixed solvent (propyl carbinol: in the toluene=1:3); divide water backflow 6h; decompression steams solvent, column chromatography (sherwood oil: acetone=4:1) the red-brown solid, productive rate 24%. 1H NMR (CDCl 3, 400MHz, ppm)δ: 10.96 (s, 2H), 5.80 (s, 2H), 5.64 (s, 1H), 3.24 (d, J = 7.4 Hz, 4H), 2.12 (m, 2H), 0.92 (d, J = 6.6Hz, 12H)。
(4) preparation of the sour 6a of asymmetric side
4a 0.6250g (1.7mmol), 5a 0.4035g (1.7mmol), (toluene: propyl carbinol=1:1 v/v), divides water backflow 13h to the 80mL mixed solvent, and decompression steams solvent, column chromatography (CH 2Cl 2: CH 3OH=50:1), recrystallization (methylene chloride) gets golden yellow solid 0.80g, productive rate 23%.m.p.198-199℃， 1H NMR (CDCl 3, 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= 8.8 Hz, 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 the sour 6b of asymmetric side
Figure GDA00003007562115
(1) preparation of compound 4a is with embodiment 1.
(2) preparation of the sour 6b of asymmetric side
4a 1.00g (2.8mmol), (synthetic method is seen Dyes and Pigments. 2003. 59 to 5b 0.68g (2.8mmol), 63-69.), (toluene: propyl carbinol=1:1 v/v), divides water backflow 13h to the 80mL mixed solvent, decompression steams solvent, column chromatography (CH 2Cl 2: CH 3OH=50:1), recrystallization (methylene chloride) gets bright green crystal 6 b 0.88g, productive rate 54%. 1H NMR (CDCl 3, 400MHz, ppm)δ: 12.48 (s, 2H), 8.19 (d, J = 8.4Hz, 1H), 8.04 (s, 1H), 7.92 (dd, J = 9.2, 9.2Hz, 2H), 7.60 (t, J = 7.6 Hz , 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 the sour 6c of asymmetric side
Figure GDA00003007562116
(1) preparation of compound 4a is with embodiment 1.
(2) 5-9H-carbazole-9-phenyl-1, the preparation of 3-glycol 5c
Carbazole 5.00g (30mmol), 3,5-dimethoxy bromobenzene 7.80g (36mmol), the Pd of 3% molar weight (OAc) 2, the P of 6% molar weight (t-Bu) 3 .BF 4, the sodium tert-butoxide of 1.5 times of molar weights adds in the 200mL toluene, 110 ℃ of heating 12h, filter, filtrate decompression is revolved and is desolventized, column chromatography (PE:EA), the sherwood oil recrystallization gets white needle-like crystals 9-(3,5-dimethoxy-phenyl)-9H-carbazole 6.60g, productive rate 73%. 1H NMR (CDCl 3, 400 MHz, ppm) δ: 8.13 (d, J = 8.0 Hz, 2H), 7.48 (d, J = 7.6 Hz, 2H), 7.41 (t, J = 7.6 Hz, 2H), 7.29 (t, J = 7.6 Hz, 2H), 6.72 (s，2H), 6.56 (s, 1H), 3.84 (s, 6H)。
9-(3,5-dimethoxy-phenyl)-and 9H-carbazole 1.00g (3.30mmol) adding 40mL anhydrous methylene chloride, ice bath slowly drips the anhydrous methylene chloride solution that 34mL contains boron tribromide 8.26g (33.00mmol) down, after dropwising, naturally be warming up to room temperature, stir 36h.In the reaction solution impouring 150mL frozen water, use dichloromethane extraction, water washing, the saturated sodium carbonate washing, drying concentrates, and column chromatography gets white powder 0.80g, productive rate 88%. 1H NMR (CDCl 3, 400 MHz, ppm) δ：8.12 (d, J = 8.0 Hz, 2H), 7.49 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 8.0 Hz, 2H), 7.25 (t, J = 7.6 Hz, 2H), 6.63 (s, 2H), 6.44 (s, 1H)。
(3) preparation of the sour 6c of asymmetric side
4a 1.00g (2.8mmol), 5c 0.77g (2.8mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), divide water backflow 13h, decompression steams solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride) gets glassy yellow crystal 0.35g, productive rate 20%. 1H NMR (DMSO-d 6, 400MHz, ppm)δ: 12.20 (s, 2H), 8.44 (d, J = 8.4 Hz, 1H), 8.24 (d, J = 7.6 Hz, 2H), 8.23 (d, J = 9.2 Hz, 1H), 8.17 (d, J = 8.0 Hz, 1H), 8.08 (d, J = 9.4 Hz, 1H), 7.78-7.73 (m, 3J = 7.2 Hz, 4J = 0.8 Hz, 1H), 7.68 (t, J = 7.2 Hz, 1H), 7.60(d, J = 8.4 Hz, 2H), 7.51-7.46 (m, 3J = 7.2 Hz, 4J = 0.8 Hz, 2H), 7.34-7.30 (m, 3J = 7.2 Hz, 4J = 0.4 Hz, 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 = 7.2 Hz, 3H)。
Embodiment 4: the preparation of the sour 6d of asymmetric side
Figure GDA00003007562117
(1) preparation of compound 1 is with embodiment 1.
(2) ring fourth-3-alkene-1 methyl 3-oxyethyl group-4-((3-ethyl naphtho-[2,1-d] thiazoles-2 (3H)-subunit)), the preparation of 2-diketone 3b
2b 2.52g (7.06mmol) (synthetic method is seen J. Org. Chem. 1995,60,2391-2395.) add the 20mL mixed solvent (triethylamine: ethanol=1:8, v/v), reflux 30min.Drip 1 1.20g (7.06mmol), back flow reaction 15min, decompression steams solvent, and column chromatography (PE:EA=8:1), ethyl alcohol recrystallization get orange-yellow crystal 1.98g, productive rate 80%. 1H NMR (CDCl 3, 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, 1H), 4.96 (q, J = 7.2Hz, 2H), 3.83 (q, J = 7.2Hz, 2H), 1.49 (t, J = 7.2Hz, 3H), 1.93 (t, J = 7.2Hz, 3H)。
(3) methyl 3-((3-ethyl naphtho-[2,1-d] thiazoles-2 (3H)-subunit))-and 4-hydroxyl ring fourth-3-alkene-1, the preparation of 2-diketone 4b
3b 1.84g (5.24mmol) adds the 40mL dehydrated alcohol, and reflux state adds 3mL 40% NaOH, reaction 30min down, decompression is revolved and is desolventized, and resistates is dissolved in 20mL water, drips saturated citric acid to PH=3 ~ 4, yellow mercury oxide is separated out, filter yellow powder 1.02g, productive rate 60%. 1H NMR (DMSO-d 6, 400MHz, ppm)δ: 8.21 (d, J = 8.8 Hz, 1H), 8.01 (d, J = 8.4Hz, 1H), 7.79 (d, J = 8.4 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.25 (d, J = 8.8 Hz, 1H), 7.14 (t, J = 7.6 Hz, 1H), 5.38 (s, 1H), 4.57 (q, J = 7.2 Hz, 2H), 1.84 (t, J = 7.2 Hz, 3H)。
(4) preparation of compound 5a is with embodiment 1.
(5) preparation of the sour 6d of asymmetric side
4b 0.5694g (1.73mmol), 5a 0.4106g (1.73mmol), (toluene: propyl carbinol=1:1 v/v), divides water backflow 13h to the 80mL mixed solvent, and decompression steams solvent, column chromatography (CH 2Cl 2: CH 3OH), recrystallization (methylene chloride) must have metalluster solid 0.32g, productive rate 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 the sour 6e of asymmetric side
Figure GDA00003007562118
(1) preparation of compound 4b is with embodiment 4.
(2) preparation of compound 5b is with embodiment 2.
(3) preparation of the sour 6e of asymmetric side
4b 0.9054 (2.8mmol), 5b 0.6870g (2.8mmol), (toluene: propyl carbinol=1:1 v/v), divides water backflow 13h to the 80mL mixed solvent, and decompression steams solvent, column chromatography (CH 2Cl 2: CH 3OH=50:1), recrystallization (methylene chloride) gets golden yellow solid 0.74g, productive rate 48%. 1H NMR (CDCl 3, 400MHz, 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 = 7.6 Hz , 1H ), 7.54 (t, J = 7.2Hz, 1H), 7.30 (d, J = 8.8Hz, 1H), 5.45(s, 1H), 4.57 (q, J = 7.2 Hz, 2H), 3.30 (br, 4H), 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 the sour 6f of asymmetric side
Figure GDA00003007562119
(1) preparation of compound 4b is with embodiment 4.
(2) preparation of compound 5c is with embodiment 3.
(3) preparation of the sour 6f of asymmetric side
4b 0.9054g (2.8mmol), 5c 0.7708g (2.8mmol), 80mL mixed solvent (toluene: propyl carbinol=1:1, v/v), divide water backflow 13h, decompression steams solvent, column chromatography (PE:EA=6:1), recrystallization (methylene chloride) gets green crystal 0.44g, productive rate 27%. 1H NMR (DMSO-d 6, 400MHz, ppm)δ: 12.20 (s, 2H), 8.34 (d, J = 8.4 Hz, 1H), 8.14 (d, J = 7.6 Hz, 2H), 8.05 (d, J = 8.8 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.91 (d, J = 9.4 Hz, 1H), 7.87 (t, J = 7.6 Hz, 1H), 7.68 (t, J = 7.2 Hz, 1H), 7.63 (d, J = 8.4 Hz, 2H), 7.51 (t, J = 7.2 Hz, 2H), 7.34-7.30 (t, J = 7.2 Hz, 2H), 6.68(s, 2H), 6.35(s, 1H), 4.54 (q, J = 7.2 Hz, 2H), 1.91 (t, J = 7.2 Hz, 3H)。
Embodiment 7: the sour 6a organic solar batteries of asymmetric side preparation of devices
(1) device architecture 3 mg 6a shown in Fig. 5 a mix with 17 mg PCBM, add 1 mL chloroform dissolving, by the spin coating mode through MoO 3Prepare film on the ito glass substrate of modified, vacuum evaporation LiF and Al prepare negative electrode then.White light 1.5 G(100 mW/cm 2) shine down, device photoelectric transformation efficiency (PCE) is 2.24%.
(2) device architecture 6a chloroformic solution of 1 mg/mL shown in Fig. 5 b is spin-coated on through MoO 3On the ito glass substrate of modified, vacuum evaporation C successively again 60Layer, BCP layer and Al electrode layer.White light 1.5 G(100 mW/cm 2) shine down, device photoelectric transformation efficiency (PCE) is 4.23%.
Figure GDA00003007562120
Embodiment 8: the sour 6c organic solar batteries of asymmetric side preparation of devices
(1) device architecture 3 mg 6c shown in Fig. 5 a mix with 17 mg PCBM, add 1 mL chloroform dissolving, by the spin coating mode through MoO 3Prepare film on the ito glass substrate of modified, vacuum evaporation LiF and Al prepare negative electrode then.White light 1.5 G(100 mW/cm 2) shine down, device open circuit voltage (Voc)=1.09V, electricity conversion (PCE) is 2.20%.
(2) device architecture such as Fig. 5 b be shown in are through MoO 3Vacuum evaporation 6c thin film layer, C successively on the ito glass substrate of modified 60Layer, BCP layer and Al electrode layer.White light 1.5 G(100 mW/cm 2) shine down, device photoelectric transformation efficiency (PCE) is 4.58%.
Figure GDA00003007562121
Embodiment 9: the sour 6e organic solar batteries of asymmetric side preparation of devices
(1) device architecture 4 mg 6e shown in Fig. 5 a mix with 16 mg PCBM, add 1 mL chloroform dissolving, by the spin coating mode through MoO 3Prepare film on the ito glass substrate of modified, vacuum evaporation LiF and Al prepare negative electrode then.White light 1.5 G(100 mW/cm 2) shine down device photoelectric transformation efficiency (PCE)=1.72%.
(2) device architecture 6e chloroformic solution of 1 mg/mL shown in Fig. 5 b is spin-coated on through MoO 3On the ito glass substrate of modified, vacuum evaporation C successively again 60Layer, BCP layer and Al electrode layer.White light 1.5 G(100 mW/cm 2) shine down, device photoelectric transformation efficiency (PCE) is 3.97%.
Figure GDA00003007562122
Table 2: the device photoelectric transformation efficiency PCE (%) of the sour cyanines small molecules 6a-6f in side
The sour cyanines small molecules in side 6a 6b 6c 6d 6e 6f
The body heterojunction 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 (4)

1. a series of sour cyanines small molecules of asymmetric side with formula I structure, A, B are represented different rich electric aromatic nucleus unit,
Figure FDA0000300756201
Its constitutional features is:
Described A is any one in following group 1 or 2, wherein R 1The alkoxyl group or the carbonatoms that for hydrogen atom or fluorine atom or cyano group or phenyl or phenoxy group or carbonatoms are the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or the carbonatoms straight or branched that is 1-20 are the alkoxyphenyl radical of the straight or branched of 1-20, R 2Be that the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for carbonatoms.
Group 1:
Figure FDA0000300756202
Group 2:
Figure FDA0000300756203
Described B is any one in the following group 3 to 5,
Group 3:
Figure FDA0000300756204
In the group 3, R 1And R 2Be hydroxyl or R 1Be hydroxyl and R 2Be hydrogen atom, R 3And R 4Be that the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for carbonatoms identical or inequality.
Group 4:
Figure FDA0000300756205
In the group 4, R 1And R 2Be hydrogen atom identical or inequality or hydroxyl, R 3, R 4, R 5And R 6For hydrogen atom identical or inequality or carbonatoms are the alkyl of the straight or branched of 1-20.
Group 5:
Figure FDA0000300756206
In the group 5, R 1And R 2Be hydrogen atom identical or inequality or hydroxyl, R 3, R 4, R 5And R 6Be that the alkoxyl group of the alkyl of straight or branched of 1-20 or cycloalkyl that carbonatoms is 3-10 or the carbonatoms straight or branched that is 1-20 or phenyl or carbonatoms are the alkoxyphenyl radical of the straight or branched of 1-20 for hydrogen atom identical or inequality or carbonatoms.
2. the micromolecular preparation method of the sour cyanines of arbitrary according to claim 1 asymmetric side; it is characterized in that step and reaction conditions are: under the high-purity argon gas protection; two reaction substrates that add the equimolar amount proportioning successively, with toluene: mixing solutions propyl carbinol=1:1(volume ratio) is as solvent, and heating divides the water back flow reaction 13 h; reaction finishes; evaporating solvent carries out column chromatography for separation to doing with the resistates that obtains, and collects respective components; recrystallization gets final product, and synthetic route is as follows:
Figure FDA0000300756207
Wherein, Ar is the pairing compound of group 3-5 described in the claim 1, and its structure is:
Compound 3:
Figure FDA0000300756209
Compound 4:
Figure FDA00003007562010
Compound 5:
Figure FDA00003007562011
3. the application of the sour cyanines small molecules of arbitrary according to claim 1 asymmetric side in the photoelectric functional device.
4. as the micromolecular application of the sour cyanines of asymmetric side as described in the claim 3, it is characterized in that described photoelectric functional device is an organic solar batteries.
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