CN106810531A - Based on indenofluorene nine and condensed ring A D A type conjugated molecules and preparation method thereof - Google Patents
Based on indenofluorene nine and condensed ring A D A type conjugated molecules and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to organic photoelectrical material technical field, and in particular to a class is based on indenofluorene nine and condensed ring A D A type conjugated molecules and preparation method thereof.With indenofluorene nine, simultaneously condensed ring, as core, is bridging unit with five yuan of heteroaromatics to the present invention, and end connects the A D A type conjugated molecules of short of electricity subelement.The present invention prepares the easily separated purifying of novel, simple to operate, product, it is involved based on indenofluorene nine and condensed ring A D A type conjugated molecules have good dissolubility and stability, with spectral absorption scope and suitable level structure wide, the donor or acceptor material of organic solar batteries are expected to be used for.
Description
Technical field
The invention belongs to organic photovoltaic technical field, and in particular to a class is based on indenofluorene nine and condensed ring ring is parent nucleus, with
Five yuan of heteroaromatics are bridge linkage group, and end connects A-D-A type conjugated molecules of short of electricity subelement and preparation method thereof, and such
Application of the molecule as the electron donor or electron acceptor in photoactive layer in organic photovoltaic battery field.
Background technology
Organic solar batteries have the advantages that prepared by light weight, low cost, flexible, solution processable and large area, receive
Interest and the concern of researcher are arrived.In the recent period, polymer and small molecule solar cell quickly grow, and achieve considerable
Progressive [Adv.Mater., 2013,25,3973；Nat.Commun.,2013,4,1446；Sci.Rep.,2014,4,6813；
Nat.Commun.,2014,5,5293；Nature,2014,17,1；J.Am.Chem.Soc.2014,136,15529；
Nat.Photon.,2015,9,520；Nat.Energy,2016,1,15027].At present, based on the blending of fullerene acceptor material
The photoelectric transformation efficiency of body heterojunction (BHJ) solar cell has broken through 10%, imply that organic solar batteries are huge
Application prospect.
In terms of donor material, including polymer and small molecule donor material, system research and fast development have been obtained, it is special
It is not to be up to the photoelectric transformation efficiency of fullerene acceptor single layer of material battery based on polymer donor material in the recent period
11.7%, achieve major progress.Relative to developing rapidly for donor material, the development of acceptor material is then relatively slow.Receiving
Body material aspect, the fullerene derivate based on PCBM has big electron affinity, outstanding electronic transmission performance, energy because of it
The advantages of phase separation of nano-scale is mixed to form with donor material, occupied in acceptor material leading position [Science,
1995,270,1789；Adv.Mater.,2013,25,1038].Because such material is difficult in the visible region weaker, energy level of absorption
In regulation and control, purify more difficult the shortcomings of [Energy Environ.Sci., 2011,4,1558], the polymer of synthesizing new or small
Numerator acceptor material substitutes such material and seems particularly necessary.In the recent period, it is presented fast-developing based on condensed ring small molecule receptor material
The impetus [J.Am.Chem.Soc., 2007,129,7246；J.Am.Chem.Soc.,2016,138,375；
J.Am.Chem.Soc.,2016,138,2973；J.Am.Chem.Soc.,2016,138,4955；J.Am.Chem.Soc.,
2016,138,15011；Adv.Mater.,2016,28,4734；Adv.Mater.,2016,28,9243；Chem.Mater.,
2016,28,6770；J.Am.Chem.Soc.,2016,138,DOI:10.1021/jacs.6b08523], photoelectric transformation efficiency is
12% so is breached, shows that small molecule receptor material has more wide application prospect.
The content of the invention
In order to overcome the shortcomings of that prior art is present and defect, it is good that the present invention one class of offer absorbs strong, charge transport properties
, suitably based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is used as electron donor or electron acceptor for good and electron energy level
Material is applied in organic solar batteries.
Based on indenofluorene nine, simultaneously condensed ring, due to its rigid structure, with strong Intermolecularπ πinteraction, can obtain load higher
Stream transport factor.Think deeply based on more than, so that based on indenofluorene nine, simultaneously condensed ring is parent nucleus, five yuan of heteroaromatics are used as bridging base for the present invention
The A-D-A type conjugated molecules of electron group are haled in group, end connection, and the type molecule can be applied to as donor or acceptor material
Organic solar batteries field.
What the present invention was provided has below general formula structure based on indenofluorene nine and condensed ring A-D-A type conjugated molecules：
Wherein, n is 0~3；X=O, S or Se；R1~R4It independently is hydrogen, C1~C20Alkyl, C1~C20Alkoxy,
4- alkyl phenyls, 4- alkoxyl phenyls, 5- alkylthrophenes base, 5- alkoxy thiophenes base or 5- alkylthio group thienyls；Described 4-
Alkyl phenyl, 4- alkoxyl phenyls, 5- alkylthrophenes base, 5- alkoxy thiophenes base or 5- alkylthio group thienyls are respectively C1~C8
Alkyl, alkoxy or alkylthio group.
Drawing electron group A is from one of having structure：
R in above-mentioned A units5It is C1~C8Alkyl.
Preparation method based on indenofluorene nine and condensed ring A-D-A type conjugated molecules is：
Will be with R2Replace five yuan of fragrant heterocompound (mol ratios of the double borates of indenofluorene and the bromo- 3- methyl formates of 2- of base
1:2~10) in palladium catalyst (palladium, tetrakis triphenylphosphine palladium, one or more of two (triphenylphosphine) palladium chlorides) (indenes
And the double borates of fluorenes and palladium catalyst mol ratio are 1:0.005~1) in the presence of (5 in toluene and water mixed solution:1, v/
V) cross-coupling reaction, gained compound and corresponding active metal reagent (organolithium reagent, organomagnesium reagent, Organic Manganese are carried out
One or more) reagent carries out addition reaction, then obtains required nine and fused ring compound through cyclization, after bromo metallization with
N,N-dimethylformamide prepares corresponding nine and condensed ring dialdehyde compound.The fragrant hydridization of five yuan of the bromo- 3- methyl formates of 2- is closed
Thing refer to the bromo- thenoic acid methyl esters of 2-, the bromo- 3- methyl furoates of 2-, one kind of the bromo- 3- selenophens methyl formates of 2- or
It is various.
Will be with R1, R3, R4(mol ratio is 1 with quantitative drawing electronic unit A for nine and condensed ring dialdehyde compound of substitution base:2
~10) be added in reaction vessel, chloroform and 64 equivalent pyridines are added, carry out deoxidation treatment, heating reflux reaction 12 hours.Cooling
By extraction, dry, concentration, column chromatography, you can obtain nine and condensed ring A-D-A type conjugated molecules with 70% separation yield.
Present invention obtains a series of based on indenofluorene nine and condensed ring A-D-A type conjugated molecules and preparation method thereof, the party
Method is simple to operate, the easily separated purifying of product, be easy to modification, be easy for building complicated A-D-A types conjugated molecule, in organic light
Electrical domain has preferable application prospect.Because such condensed ring A-D-A type conjugated molecules have strong rigid coplanar structure, end
End has strong drawing electronic unit, therefore, such conjugated molecule has stronger absorbability, suitable electron energy level, is adapted to
Organic solar batteries field is applied to as electron donor or acceptor material.
Main advantages of the present invention are：
1. synthesis has good dissolubility based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, can be dissolved in big portion
Divide organic solvent, such as chloroform, dichloromethane, tetrahydrofuran and chlorobenzene.
2. synthesis has good spectral absorption scope based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, is adapted to
For organic solar battery material.
3. synthesis has suitable electrochemistry energy level based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, is adapted to use
Make electron donor or electron acceptor material.
4. synthesis based on indenofluorene nine and condensed ring A-D-A type conjugated molecules as electron acceptor material in organic solar
Energy conversion efficiency higher is obtained in battery.
Brief description of the drawings
Fig. 1 is the UV-visible absorption spectrum based on indenofluorene nine and condensed ring A-D-A type conjugated molecules DTIF-IC.
Fig. 2 is the cyclic voltammetry curve figure based on indenofluorene nine and condensed ring A-D-A type conjugated molecules DTIF-IC.
Fig. 3 is that the I-V of the organic solar batteries based on indenofluorene nine and condensed ring A-D-A type conjugated molecules DTIF-IC is bent
Line.
Specific embodiment
Explanation is further explained to present aspect below by specific embodiment.
Syntheti c route based on indenofluorene nine and condensed ring A-D-A type conjugated molecules is as follows, with the double pinacols of indenofluorene
Ester 1 is initiation material, obtains nine and fused ring compound 5 through Suzuki couplings, addition, cyclization successively.DMF is quenched after lithiumation
To intermediate 7, finally there is Knoevenagel reactions with 7 in the presence of pyridine, generation is based on indenofluorene nine and condensed ring A-D-A
Type conjugated molecule framework compound 8, detailed in Example 1-5.
Syntheti c route based on indenofluorene nine and condensed ring A-D-A type conjugated molecules
The synthetic route of the compound 3 of embodiment 1. is as follows：
Under nitrogen protection, addition compound 1 (2.0g, 2.4mmol) in 250mL there-necked flasks, compound 2 (1.3g,
6mmol), potassium carbonate (1.7g, 12mmol), 336 (0.5g), Pd (PPh3)4(0.23g, 10%mol) is dissolved in 18mL toluene/waters
(5:1), heating reflux reaction 72h, stops reaction, and ether extraction merges organic phase, saturated common salt water washing, anhydrous magnesium sulfate
Dry, suction filtration is spin-dried for solvent, and pillar layer separation obtains 1.7g yellow oils, yield 86%.1H NMR(500MHz,CDCl3)δ
7.77 (s, 1H), 7.75 (s, 1H), 7.64 (d, J=1.8Hz, 2H), 7.54 (d, J=1.1Hz, 1H), 7.52 (d, J=
1.1Hz, 1H), 7.50 (d, J=1.6Hz, 1H), 7.48 (d, J=1.6Hz, 1H), 7.44 (d, J=1.4Hz, 2H), 7.25 (s,
1H), 7.24 (s, 1H), 3.71 (s, J=1.2Hz, 6H), 2.03 (t, J=8.2Hz, 9H), 1.22-1.00 (m, 45H), 0.82-
0.75(m,15H).13C NMR(126MHz,CDCl3)δ164.05,151.69,150.86,150.63,141.86,140.37,
131.70,130.20,128.45,127.83,124.44,123.83,118.99,114.22,54.88,51.46,40.62,
31.81,30.08,29.28,29.24,23.82,22.59,14.07.
The synthetic route of the compound 4 of embodiment 2. is as follows：
Under nitrogen protection, to the 250mL tri- equipped with 4- hexyls bromobenzene (5.0g, 20.7mmol) and 100mL THF at -78 DEG C
2M butyl lithium 10mL are added dropwise in mouth bottle, low-temp reaction 1h is kept.At this temperature, in reaction solution be added dropwise compound 3 (1.77g,
2.03mmol), recover to be stirred overnight at room temperature, hydrolyze, ether is extracted three times, merge organic phase, saturated common salt water washing, anhydrous sulphur
Sour magnesium is dried.Suction filtration, is spin-dried for solvent, and pillar layer separation obtains yellow green grease 0.8g, yield 80%.1H NMR(500MHz,
CDCl3) δ 7.64 (s, 1H), 7.62 (s, 1H), 7.50 (d, J=3.0Hz, 2H), 7.32 (d, J=1.6Hz, 1H), 7.31 (d, J
=1.6Hz, 1H), 7.19 (d, J=8.2Hz, 8H), 7.14 (t, J=6.9Hz, 8H), 7.10 (d, J=5.3Hz, 2H), 6.92
(d, J=1.4Hz, 2H), 6.40 (d, J=5.3Hz, 2H), 2.65-2.61 (m, 10H), 1.63 (tt, J=12.5,6.2Hz,
17H), 1.43-1.25 (m, 40H), 1.19-0.96 (m, 61H), 0.94-0.87 (m, 21H), 0.78 (dd, J=8.9,5.3Hz,
18H).13C NMR(126MHz,CDCl3)δ151.35,150.41,145.89,145.77,144.19,141.91,141.75,
141.39,140.18,139.24,132.87,131.62,128.97,127.98,127.92,127.62,123.93,122.25,
119.58,114.02,80.80,54.69,40.16,35.67,31.90,31.83,31.79,31.59,29.96,29.25,
29.11,29.04,23.69,22.71,22.66,22.61,14.15,14.07,13.81.
The synthetic route of the compound 5 of embodiment 3. is as follows：
Compound 4 (0.8g, 0.5mmol) is added in 50mL single necked round bottom flask, CH is dried2Cl230mL, boron trifluoride
Diethyl ether solution 10mL, heating reflux reaction is overnight.Stop heating.Cooling, adds water, CH2Cl2Extraction three times, merges organic phase,
Saturated common salt water washing, anhydrous magnesium sulfate is dried.Suction filtration, rotation removes solvent, and pillar layer separation obtains yellow solid 0.57g, yield
73%.1H NMR(500MHz,CDCl3)δ7.67(s,2H),7.44(s,2H),7.37(s,2H),7.27(s,1H),7.26(s,
1H), 7.21 (d, J=8.3Hz, 8H), 7.08 (d, J=8.3Hz, 8H), 7.02 (s, 1H), 7.01 (s, 1H), 2.60-2.54
(m,8H),2.06–1.91(m,9H),1.65–1.52(m,9H),1.39–1.25(m,24H),1.19–1.00(m,40H),0.88
(m,12H),0.78–0.74(m,12H),0.70(s,8H).13C NMR(126MHz,CDCl3)δ156.04,152.77,
151.10,150.25,144.85,142.57,142.11,141.57,141.24,140.28,139.61,138.38,136.13,
134.92,128.22,128.04,127.11,123.23,117.35,113.80,113.66,62.65,54.43,40.81,
35.60,31.77,31.73,31.32,30.08,29.26,29.23,29.20,23.85,22.60,22.57,14.08,
14.04.
The synthetic route of the compound 6 of embodiment 4. is as follows：
Under nitrogen protection, compound 5 (0.57g, 0.37mmol), dry THF are added in 100mL three neck round bottom flask
10mL, is cooled to -78 DEG C, to LDA (5mL, 1.1mmol) is added dropwise in reaction bulb, keeps low-temp reaction 1h.At this temperature, to
DMF 1mL are added in reaction bulb, it is slow to recover to be stirred overnight at room temperature.Added water stopped reaction, and ether is extracted three times, merges organic phase
Saturated common salt water washing, anhydrous magnesium sulfate is dried.Suction filtration, rotation removes solvent, and pillar layer separation obtains yellow solid 0.23g, yield
40%.1H NMR(500MHz,CDCl3)δ9.83(s,2H),7.72(s,2H),7.66(s,2H),7.51(s,2H),7.50(s,
2H), 7.20 (d, J=8.2Hz, 8H), 7.11 (d, J=8.3Hz, 8H), 2.63-2.54 (m, 8H), 2.11-1.93 (m, 9H),
1.65-1.53 (m, 9H), 1.39-1.24 (m, 24H), 1.20-1.06 (m, 40H), 0.87 (t, J=6.8Hz, 12H), 0.74
(t, J=6.8Hz, 12H), 0.69 (s, 8H)13C NMR(126MHz,CDCl3)δ182.95,156.65,156.43,154.39,
152.12,151.90,151.13,145.32,141.77,141.57,140.48,128.50,127.87,117.83,115.56,
114.29,62.86,54.66,40.68,35.58,31.73,31.71,31.31,29.97,29.22,29.17,23.86,
22.59,22.56,14.07,14.02.
Embodiment 5. is based on indenofluorene nine and the synthetic route of condensed ring A-D-A types conjugated molecule 8 (DTIF-IC) is as follows：
Addition compound 6 (70mg, 0.044mmol) in 100mL single necked round bottom flask, compound 7 (43mg,
0.22mmol), CHCl310mL, pyridine 0.32mL, solution carries out deoxidation treatment, is heated to back flow reaction 12h.It is cooled to room
Temperature, is washed three times, and organic phase is dried with anhydrous magnesium sulfate.Suction filtration, is spin-dried for solvent, and pillar layer separation obtains bluish violet solid
60mg, yield 70%.1H NMR(500MHz,CDCl3)δ8.92(s,2H),8.70(s,1H),8.69(s,1H),7.95–7.92
(m, 2H), 7.79-7.71 (m, 8H), 7.66 (s, 2H), 7.54 (s, 2H), 7.21 (d, J=8.3Hz, 8H), 7.13 (d, J=
8.3Hz,8H),2.62–2.54(m,8H),2.12–1.96(m,9H),1.66–1.57(m,9H),1.35-1.29(m,24H),
1.18-1.02 (m, 40H), 0.87 (t, J=6.8Hz, 12H), 0.76 (t, J=7.0Hz, 12H), 0.73-0.70 (m, 8H)13C
NMR(126MHz,CDCl3)δ188.45,161.22,152.63,143.83,142.06,141.29,137.04,134.21,
128.61,127.91,63.07,54.78,35.59,31.73,31.71,31.32,30.01,29.23,29.20,29.15,
22.59,22.57,14.08,14.03.
UV-visible absorption spectrum such as Fig. 1 institutes based on indenofluorene nine and condensed ring A-D-A type conjugated molecules DTIF-IC
Show；Cyclic voltammetry curve is as shown in Figure 2；The I-V curve of prepared organic solar batteries is as shown in figure 3, measure device
Short circuit current JscIt is 13.46mA cm-2, open-circuit voltage VocIt is 0.94V, fill factor, curve factor FF is 56.5%, energy conversion efficiency PCE
It is 7.14%.
The preparation and performance test of solar photovoltaic device：By commercially available tin indium oxide (ITO) electro-conductive glass successively
It is cleaned by ultrasonic with deionized water, acetone, semiconductor washing solution, deionized water, isopropanol, is placed on drying in vacuum drying chamber.
Spin coating ZnO precursor solution on clean ITO, ZnO thickness is 40nm, and substrate places thermal annealing 60 minutes on 200 DEG C of warm tables.Will
Glass/ITO/ZnO substrates are transferred in the glove box full of nitrogen, spin coating water alcohol solubility cathodic modification layer PFN.By embodiment 5
A-D-A type conjugated molecule DTIF-IC and polymer donor material PTB7-Th (weight is than being all 1.3:1) blend solution (20
~30mg/ml) it is spun on ITO/ZnO (40nm)/PFN (10nm), 70 DEG C of thermal annealings 10 minutes.Then device is transferred to very
In sky evaporation chamber, using vacuum deposition method (3 × 10-5Pa) deposition 10nm thick MoO3With 100nm thickness metals Al.Device architecture
For：Glass/ITO (130nm)/ZnO (40nm)/PFN (10nm)/active layer (90nm)/MoO3(10nm)/Al (100nm), photovoltaic
The effective area of device is 0.16cm2。
With equipped with AM1.5 optical filter Newport 500W xenon lamps as simulated solar light source, in 100mW/cm2It is right under light intensity
Device carries out photovoltaic performance test, and light intensity is calibrated by standard monocrystalline silicon solar cell；I-V curve uses Keithley
2400 measure, and are controlled by computer by Labview softwares.
The I-V of the organic solar batteries based on the miscellaneous condensed ring A-D-A types conjugated molecule DTIFC-IC of five yuan of virtues of dibenzo is bent
Line is as shown in Figure 3.
The structure of the polymer donor material PBT7-Th used by the present invention is as follows：
Claims (8)
1. it is a kind of based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that its structural formula is：
Wherein, n is 0~3；X=O, S or Se；R1~R4It independently is hydrogen, C1~C20Alkyl, C1~C20Alkoxy, 4- alkane
Base phenyl, 4- alkoxyl phenyls, 5- alkylthrophenes base, 5- alkoxy thiophenes base or 5- alkylthio group thienyls；
Drawing electron group A is from one of having structure：
R in above-mentioned A units5It is C1~C8Alkyl.
2. as claimed in claim 1 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described 4- alkane
Alkane in base phenyl, 5- alkylthrophenes base, 4- alkoxyl phenyls, 5- alkoxy thiophenes, 5- alkylthio group thienyls is C1~C8。
3. as claimed in claim 1 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described n is 0
~3；X=S；R1~R4It independently is hydrogen, C1~C8Alkyl or 4- hexyl phenyl.
4. as claimed in claim 1 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described n is 0
~3；X=S；R1~R4It independently is hydrogen, C1~C8Alkoxy or 4- hexyl phenyl.
5. the indenofluorene nine as described in Claims 1 to 4 is any and condensed ring A-D-A type conjugated molecules, it is characterised in that preparation side
Method is：
It is 1 by mol ratio:2~10 with R2Replace five yuan of fragrant hydridization of the double borates of indenofluorene and the bromo- 3- methyl formates of 2- of base
Compound, in the presence of palladium catalyst, in volume ratio be 5:Cross-coupling reaction, institute are carried out in 1 toluene and water mixed solution
Obtain compound carries out addition reaction with corresponding active metal reagent, then obtains required nine and fused ring compound through cyclization, through bromo
Metallization afterwards prepares corresponding nine and condensed ring dialdehyde compound with N,N-dimethylformamide；
It is 1 by mol ratio:2~10 carry R1、R3、R4Nine and condensed ring dialdehyde compound of substitution base add with quantitative drawing electronic unit A
To in reaction vessel, chloroform and 64 equivalent pyridines are added, carry out deoxidation treatment, heating reflux reaction 12 hours, through extraction after cooling
Take, dry, concentrating, column chromatography, you can obtain nine and condensed ring A-D-A type conjugated molecules with 70% separation yield.
6. as claimed in claim 5 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described 2-
The fragrant heterocompound of five yuan of bromo- 3- methyl formates refers to the bromo- thenoic acid methyl esters of 2-, the bromo- 3- methyl furoates of 2-, 2-
One or more in bromo- 3- selenophens methyl formate.
7. as claimed in claim 5 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described palladium is urged
Agent refers to one or more in palladium, tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chlorides.
8. as claimed in claim 5 based on indenofluorene nine and condensed ring A-D-A type conjugated molecules, it is characterised in that described is active
Metal reagent refers to one or more in organolithium reagent, organomagnesium reagent, Organic Manganese reagent.
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