CN113929705A - Conjugated organic compound, preparation method and application thereof - Google Patents

Conjugated organic compound, preparation method and application thereof Download PDF

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CN113929705A
CN113929705A CN202111160777.0A CN202111160777A CN113929705A CN 113929705 A CN113929705 A CN 113929705A CN 202111160777 A CN202111160777 A CN 202111160777A CN 113929705 A CN113929705 A CN 113929705A
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carbon atoms
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CN113929705B (en
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葛子义
杨道宾
杨顺成
闫鹏宇
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Ningbo Institute of Material Technology and Engineering of CAS
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    • C07D513/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00
    • C07D513/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for in groups C07D463/00, C07D477/00 or C07D499/00 - C07D507/00 in which the condensed system contains four or more hetero rings
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    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention provides a conjugated organic compound, a preparation method and application thereof, and relates to the technical field of photoelectric functional devices. Compared with the prior art, the conjugated organic compound has good absorption in a visible light region, can form good complementation with the absorption of a low band gap acceptor material, is beneficial to obtaining high short-circuit current and improving the photoelectric conversion efficiency.

Description

Conjugated organic compound, preparation method and application thereof
Technical Field
The invention relates to the technical field of photoelectric functional devices, in particular to a conjugated organic compound, a preparation method and application thereof.
Background
Solar energy is one of the most important clean and renewable energy sources, and is an important solution for dealing with global energy transformation and achieving the aim of carbon neutralization. The novel solar cell represented by the organic solar cell (OSCs for short) has the remarkable advantages of simple preparation, low cost, wide material selection, capability of being made into a flexible device and the like, and has great application prospect in the fields of portable charging equipment, photovoltaic building integration and flexible wearable electronic equipment. In order to continue to advance the practical application of organic solar cell technology, improving device efficiency remains one of the major tasks and challenges facing today, and developing new high-efficiency organic photovoltaic materials is central.
Disclosure of Invention
The invention solves the problem of improving the photoelectric conversion efficiency of the existing photoelectric functional device.
In order to solve the above problems, the present invention provides a conjugated organic compound, which uses a cyano-indenopyridine unit as an end group, and the structural formula of the conjugated organic compound is shown as formula one, wherein formula one is:
Figure BDA0003290116200000011
wherein Ar is a unit comprising a pi conjugated structure; r1And R2Comprises the same or different hydrogen atoms, straight chain or branched chain alkyl with 2-20 carbon atoms or cycloalkyl with 5-9 carbon atoms; x and Y comprise the same or different H, F, Cl or Br.
Preferably, the structural formula of Ar is shown as formula II, and the formula II is as follows:
Figure BDA0003290116200000021
wherein R comprises linear or branched alkyl with 2-20 carbon atoms or linear alkylbenzene with 2-20 carbon atoms.
Preferably, the structural formula of Ar is shown as formula III, and the formula III is as follows:
Figure BDA0003290116200000022
wherein R is3Comprises 2-2 carbon atoms0 linear or branched alkyl group or linear alkylbenzene having 2 to 20 carbon atoms; r4And R5Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
Preferably, the structural formula of Ar is represented by formula iv, which is:
Figure BDA0003290116200000023
wherein R is6Comprises a linear or branched alkyl with 2-20 carbon atoms or a linear alkylbenzene with 2-20 carbon atoms; r7Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
Preferably, the structural formula of Ar is shown as formula five, and the formula five is as follows:
Figure BDA0003290116200000031
wherein R is8And R9Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r10And R11Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
Preferably, the structural formula of Ar is represented by formula six, wherein formula six is:
Figure BDA0003290116200000032
wherein R is12And R13Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r14Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
Compared with the prior art, the conjugated organic compound provided by the invention has the advantage that the conjugated organic compound is a conjugated organic compound taking a cyanoindenopyridine unit as an end group. The conjugated organic compound of A-Ar-A type is formed by using a pi conjugated aromatic group as a central unit (Ar) and a cyanoindenopyridine group as an electron-withdrawing end group unit (A). The cyano indenopyridine unit has a larger pi conjugated structure, so that molecules of the cyano indenopyridine unit have better pi-pi accumulation, the carrier transmission performance of the molecules is improved, and the photoelectric conversion efficiency of the organic solar cell is improved. In addition, the electron-withdrawing ability of the cyano indeno-pyridine unit is obviously weaker than that of the cyano indeno-ketone unit, so that the energy level of a conjugated molecule constructed by the cyano indeno-pyridine unit is improved, the energy gap is increased, and the cyano indeno-pyridine unit is more suitable for being used as an organic solar cell donor material. And the obtained medium band gap molecules are blended with the low band gap non-fullerene acceptor material, and the absorption spectrum of the film can cover the solar spectrum as much as possible, so that more solar photons can be captured, and finally the efficiency of the device is improved. Therefore, the conjugated organic compound has good absorption in a visible light region, can form good complementation with the absorption of a low band gap acceptor material, and is beneficial to obtaining high short-circuit current.
In order to solve the above problems, the present invention also provides a method for preparing the conjugated organic compound, comprising the steps of:
step S1, under the protection of inert gas, dissolving 1 molar equivalent of aldehyde compound and 5-10 times of excessive cyano-indanone derivative in a reaction solvent, dripping 3-5 times of excessive organic amine at room temperature, heating and refluxing for reaction for 12-36h, and obtaining a primary product after the reaction solvent is evaporated to dryness;
and step S2, performing column chromatography separation, drying and recrystallization on the primary product obtained in the step S1 to obtain the conjugated organic compound with the purity of more than 99.5%.
In order to solve the above problems, the present invention also provides another method for preparing the conjugated organic compound, comprising the steps of:
step T1, under the protection of inert gas, dissolving 1 molar equivalent of the compound a in a reaction solvent, dripping organic amine with the excess amount of 3-5 times at room temperature, heating and refluxing for 12-36h, and obtaining an initial product after the reaction solvent is evaporated to dryness;
and step T2, performing column chromatography separation, drying and recrystallization on the primary product obtained in the step T1 to obtain a conjugated organic compound with the purity of more than 99.5%, wherein the structural formula of the compound a is shown as formula seven, and the formula seven is as follows:
Figure BDA0003290116200000041
wherein Ar is a unit comprising a pi conjugated structure.
The reaction solvent includes chloroform.
The preparation method of the conjugated organic compound of the present invention has the same advantages as the above conjugated organic compound over the prior art, and is not described herein again.
In order to solve the problems, the invention also provides application of the conjugated organic compound in preparing a photoelectric functional device, wherein the photoelectric functional device is an organic solar cell.
The conjugated organic compound provided by the invention is used as an organic solar cell donor material, can form good complementation with the absorption of a low band gap acceptor material, is beneficial to obtaining high short-circuit current, and realizes the improvement of device efficiency.
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FIG. 1 is a first flow chart of a method for preparing a conjugated organic compound according to an embodiment of the present invention;
FIG. 2 is a second flow chart of a method for preparing a conjugated organic compound according to an embodiment of the present invention;
fig. 3 is a schematic structural diagram of an organic solar cell device in an embodiment of the present invention.
Description of reference numerals:
1-ITO glass; 2-PEDOT, PSS or ZnO; 3-a blended film of the conjugated organic compound and Y6; 4-MoO3Or PDINO; 5-Al or Ag electrode。
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
It is noted that throughout the description of the embodiments of the present application, the description of the term "some embodiments" means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. Throughout this specification, the schematic representations of the terms used above do not necessarily refer to the same implementation or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The embodiment of the invention provides a conjugated organic compound, which takes a cyano-indenopyridine unit as an end group, and the structural formula of the conjugated organic compound is shown as a formula I, wherein the formula I is as follows:
Figure BDA0003290116200000051
wherein Ar is a unit comprising a pi conjugated structure; r1And R2Comprises the same or different hydrogen atoms, straight chain or branched chain alkyl with 2-20 carbon atoms or cycloalkyl with 5-9 carbon atoms; x and Y comprise the same or different H, F, Cl or Br.
The conjugated organic compound described in the embodiment of the present invention is a conjugated organic compound having a cyanoindenopyridine unit as an end group. The conjugated organic compound of A-Ar-A type is formed by using a pi conjugated aromatic group as a central unit (Ar) and a cyanoindenopyridine group as an electron-withdrawing end group unit (A). The cyano indenopyridine unit has a larger pi conjugated structure, so that molecules of the cyano indenopyridine unit have better pi-pi accumulation, the transmission performance of the molecules is improved, and the efficiency of an organic solar cell device is improved. In addition, the electron-withdrawing ability of the cyano-indeno-pyridine unit is obviously weaker than that of the cyano-indeno-ketone unit, so that the energy level of a conjugated molecule constructed by the cyano-indeno-pyridine unit is improved, the energy gap is improved, and the cyano-indeno-pyridine unit is more suitable for serving as a donor material in an organic solar cell.
It should be noted that, in this embodiment, the specific structure of Ar is not limited as long as Ar includes a pi conjugated structure.
In some preferred embodiments, Ar has a structural formula shown in formula II, wherein formula II is:
Figure BDA0003290116200000061
wherein R comprises linear or branched alkyl with 2-20 carbon atoms or linear alkylbenzene with 2-20 carbon atoms.
In some preferred embodiments, Ar has a structural formula shown in formula III, wherein formula III is:
Figure BDA0003290116200000062
wherein R is3Comprises a linear or branched alkyl with 2-20 carbon atoms or a linear alkylbenzene with 2-20 carbon atoms; r4And R5Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
In some preferred embodiments, Ar has a structural formula shown as formula IV:
Figure BDA0003290116200000063
wherein R is6Comprises a linear or branched alkyl with 2-20 carbon atoms or a linear alkylbenzene with 2-20 carbon atoms; r7Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
In some preferred embodiments, Ar has a structural formula shown as formula V, wherein formula V is:
Figure BDA0003290116200000071
wherein R is8And R9Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r10And R11Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
In some preferred embodiments, Ar has a structural formula shown as formula six, wherein formula six is:
Figure BDA0003290116200000072
wherein R is12And R13Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r14Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
Therefore, the conjugated organic compound provided in the embodiment of the present invention uses a pi-conjugated aromatic group as a central unit (Ar) and a cyanoindenopyridine group as an electron-withdrawing end unit (a), so as to form an a-Ar-a type conjugated organic compound. The conjugated organic compound disclosed by the embodiment of the invention has good absorption in a visible light region, can form good complementation with the absorption of a low band gap acceptor material, and is beneficial to obtaining high short-circuit current.
As shown in fig. 1, another embodiment of the present invention provides a method for preparing the conjugated organic compound, including the steps of:
step S1, under the protection of inert gas, dissolving 1 molar equivalent of aldehyde compound and 5-10 times of excessive cyano-indanone derivative in a reaction solvent, dripping 3-5 times of excessive organic amine at room temperature, heating and refluxing for reaction for 12-36h, and obtaining a primary product after the reaction solvent is evaporated to dryness;
and step S2, performing column chromatography separation, drying and recrystallization on the primary product obtained in the step S1 to obtain the conjugated organic compound with the purity of more than 99.5%.
The synthetic route of the preparation method of the conjugated organic compound described in this example is as follows:
Figure BDA0003290116200000081
wherein Ar is a unit comprising a pi conjugated structure; r1And R2Comprises the same or different hydrogen atoms, straight chain or branched chain alkyl with 2-20 carbon atoms or cycloalkyl with 5-9 carbon atoms; x and Y comprise the same or different H, F, Cl or Br.
In this embodiment, the number of recrystallization is not limited as long as the purity of the conjugated organic compound can be ensured to be the maximum, and in some preferred embodiments, the recrystallization is performed for 2 to 3 times, which can save cost, improve efficiency, and ensure the maximum purity of the conjugated organic compound.
In this embodiment, the specific kind of the reaction solvent is not limited as long as the aldehyde compound and the cyano indanone derivative can be dissolved and then easily evaporated to dryness, and in some preferred embodiments, the reaction solvent is chloroform, which has good solubility, easily available materials and low cost.
As shown in fig. 2, another embodiment of the present invention also provides another method for preparing the conjugated organic compound, including the steps of:
step T1, under the protection of inert gas, dissolving 1 molar equivalent of the compound a in a reaction solvent, dripping organic amine with the excess amount of 3-5 times at room temperature, heating and refluxing for 12-36h, and obtaining an initial product after the reaction solvent is evaporated to dryness;
and step T2, performing column chromatography separation, drying and recrystallization on the primary product obtained in the step S1 to obtain a conjugated organic compound with the purity of more than 99.5%, wherein the structural formula of the compound a is shown as formula seven, and the formula seven is as follows:
Figure BDA0003290116200000091
wherein Ar is a unit comprising a pi conjugated structure.
The synthetic route of the preparation method of the conjugated organic compound described in this example is as follows:
Figure BDA0003290116200000092
wherein Ar is a unit comprising a pi conjugated structure; r1And R2Comprises the same or different hydrogen atoms, straight chain or branched chain alkyl with 2-20 carbon atoms or cycloalkyl with 5-9 carbon atoms; x and Y comprise the same or different H, F, Cl or Br.
In this embodiment, the number of recrystallization is not limited as long as the purity of the conjugated organic compound can be ensured to be the maximum, and in some preferred embodiments, the recrystallization is performed for 2 to 3 times, which can save cost, improve efficiency, and ensure the maximum purity of the conjugated organic compound.
In this embodiment, the specific kind of the reaction solvent is not limited as long as the compound a can be dissolved and is easy to be evaporated to dryness, and in some preferred embodiments, the reaction solvent is chloroform, which has good solubility, easily available materials and low cost.
The preparation method of the conjugated organic compound of the present invention has the same advantages as the above conjugated organic compound over the prior art, and is not described herein again.
The embodiment of the invention also provides application of the conjugated organic compound in preparing a photoelectric functional device, wherein the photoelectric functional device is an organic solar cell.
In this embodiment, the structure of the organic solar cell device is shown in fig. 3, wherein 1 is ITO glass; 2 PEDOT, PSS or ZnO, with a thickness of 20-40 nm; 3 is a blended film of the conjugated organic compound and Y6, the thickness is 80-120 nm; 4 is aMoO3Or PDINO with a thickness of 5-10 nm; 5 is Al or Ag electrode with thickness of 80-100 nm.
Wherein the structural formula of Y6 is shown as formula VIII, and the formula VIII is:
Figure BDA0003290116200000101
wherein the structural formula of PDINO is shown as formula nine, and the formula nine is as follows:
Figure BDA0003290116200000102
the conjugated organic compound provided by the invention is applied to an organic solar cell as a donor material, can form good complementation with the absorption of a low band gap acceptor material, is beneficial to obtaining high short-circuit current, and realizes the improvement of device efficiency.
Example 1
This example provides a method for preparing a conjugated organic compound Fu-1, comprising the following steps:
in a two-necked flask, aldehyde compound (0.57g,0.80mmol), cyanoindanone (1.10g,4.80 mmol) and 60mL of chloroform are added, and 1.0mL of piperidine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 24 hours. After the reaction, the reaction mixture was dropped into 600mL of methanol to precipitate, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane ═ 1:1) to obtain a crude product. Recrystallization was performed twice using methanol to chloroform (volume ratio, 1:4) as a mixed solvent, and 0.52g of Fu-1 was finally obtained as a reddish brown solid. The synthetic route is as follows:
Figure BDA0003290116200000103
the nuclear magnetic detection result of the conjugated organic compound Fu-1 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:9.58(s,2H),8.31(q,J＝6.8Hz,2H),7.61 (t,J＝7.6Hz,2H),4.64(d,J＝7.6Hz,4H),4.07(t,J＝5.2Hz,8H),2.16-2.13(m,2H), 1.90-1.82(m,12H),1.15-0.79(m,32H),0.70-0.64(m,12H).TOF-MS(APCI): m/z[M+H]1309.5257。
example 2
This example provides another method for preparing a conjugated organic compound Fu-1, comprising the steps of:
in a two-neck flask, a reaction substrate (0.30g,0.26mmol) and 50mL of chloroform are added, and 0.5mL of piperidine is added dropwise under nitrogen at room temperature, and the mixture is refluxed for 24 hours. After the reaction, the reaction mixture was dropped into 600mL of methanol to precipitate, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane ═ 1:1) to obtain a crude product. Recrystallization was performed twice using methanol to chloroform (volume ratio, 1:4) as a mixed solvent, and 0.52g of Fu-1 was finally obtained as a reddish brown solid. The synthetic route is as follows:
Figure BDA0003290116200000111
example 3
This example provides a method for preparing a conjugated organic compound Fu-2, comprising the following steps:
in a two-neck flask, aldehyde compound (60mg,0.08mmol), cyanoindanone (110mg,0.48 mmol) and 20mL chloroform are added, and 0.1mL of LN-ethylheptylamine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 24 h. After the reaction, the reaction mixture was dropped into 100mL of methanol to precipitate, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane: 1) to obtain a crude product. Recrystallization was performed twice using methanol to chloroform (volume ratio, 1:1) as a mixed solvent to obtain 50mg of a reddish brown solid Fu-2. The synthetic route is as follows:
Figure BDA0003290116200000121
the nuclear magnetic detection result of the conjugated organic compound Fu-2 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:9.60(s,2H),8.42(q,J＝6.8Hz,2H),7.61 (t,J＝7.6Hz,2H),4.64(d,J＝7.2Hz,4H),4.02(q,J＝6.8Hz,4H),3.89(t,J＝7.6Hz, 4H),2.17-2.13(m,2H),1.93-1.86(m,4H),1.56-1.34(m,22H),1.17-0.88(m, 38H),0.70-0.64(m,12H).TOF-MS(APCI):m/z[M+H]1425.6777。
example 4
This example provides a method for preparing a conjugated organic compound Fu-3, comprising the following steps:
in a two-neck flask, aldehyde compound (60mg,0.08mmol), cyanoindanone (110mg,0.48 mmol) and 20mL chloroform are added, and 0.1mL of heptylamine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 36 h. After the reaction, the reaction mixture was dropped into 100mL of methanol to precipitate, and the obtained solid was separated and purified by column chromatography (eluent: petroleum ether: dichloromethane: 1) to obtain a crude product. The recrystallization was performed twice using methanol to chloroform (volume ratio, 1:1) as a mixed solvent to obtain 40mg of a reddish brown solid Fu-3. The synthetic route is as follows:
Figure BDA0003290116200000122
the nuclear magnetic detection result of the conjugated organic compound Fu-3 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:9.64(s,2H),8.11(q,J＝6.8Hz,2H),7.62 (t,J＝7.6Hz,2H),5.82(t,J＝4.8Hz,2H),4.64(d,J＝7.2Hz,4H),3.84(q,J＝7.6Hz, 4H),2.18-2.12(m,2H),1.85-1.78(m,4H),1.55-1.36(m,17H),1.17-0.77(m, 38H),0.70-0.64(m,12H).TOF-MS(APCI):m/z[M+H]1369.6298。
example 5
This example provides a method for preparing a conjugated organic compound Fu-4, comprising the following steps:
in a two-neck flask, aldehyde compound (225mg,0.25mmol), cyanoindanone (182mg,1.0 mmol) and 50mL chloroform are added, and 0.5mL of N-ethylheptylamine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 36 h. After the reaction, the reaction solution was dropped into 500mL of methanol to carry out precipitation, and the obtained solid was subjected to column chromatography separation and purification (eluent: petroleum ether: chloroform: 3:2) to obtain a crude product. The recrystallization was performed twice using methanol to chloroform (volume ratio, 1:1) as a mixed solvent to obtain 180 mg of a reddish brown solid Fu-4. The synthetic route is as follows:
Figure BDA0003290116200000131
the nuclear magnetic detection result of the conjugated organic compound Fu-4 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:9.65(s,1H),8.36-8.30(m,2H), 7.56-7.51(m,2H),4.66(d,J＝6.0Hz,2H),4.62(d,J＝6.0Hz,2H),3.96-3.90(m, 4H),3.88-3.82(m,4H),2.83(d,J＝7.2Hz,2H),2.18-2.10(m,2H),1.94-1.86(m, 4H),1.51-0.61(m,89H)。
example 6
This example provides a method for preparing a conjugated organic compound Fu-5, comprising the following steps:
in a two-neck flask, aldehyde compound (332mg,0.40mmol), cyanoindanone (460mg,2.0 mmol) and 50mL chloroform are added, and 1.0mL of LN-ethylheptylamine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 24 h. After the reaction, the reaction solution was dropped into 500mL of methanol to carry out precipitation, and the obtained solid was subjected to column chromatography separation and purification (eluent: petroleum ether: chloroform: 3:2) to obtain a crude product. The recrystallization was performed twice using methanol to chloroform (volume ratio, 1:2) as a mixed solvent to obtain 250mg of a reddish brown solid Fu-5. The synthetic route is as follows:
Figure BDA0003290116200000141
the nuclear magnetic detection result of the conjugated organic compound Fu-5 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:9.68(s,2H),8.39(q,J＝6.8Hz,2H),7.59 (t,J＝8.0Hz,2H),4.69(d,J＝6.0Hz,4H),3.97(q,J＝6.8Hz,4H),3.88(t,J＝6.0Hz, 4H),2.18-2.10(m,2H),1.94-1.86(m,4H),1.51-1.37(m,22H),1.15-0.81(m, 38H),0.69-0.61(m,12H).TOF-MS(APCI):m/z[M+H]1537.6455。
example 7
This example provides a method for preparing a conjugated organic compound Fu-6, comprising the following steps:
in a two-neck flask, aldehyde compound (105mg,0.10mmol), cyanoindanone (115mg,0.50 mmol) and 25mL chloroform are added, and 0.4mL of LN-ethylheptylamine is added dropwise under nitrogen protection at room temperature, and the mixture is refluxed for 30 h. After the reaction, the reaction solution was dropped into 200mL of methanol to carry out precipitation, and the obtained solid was subjected to column chromatography separation and purification (eluent: petroleum ether: chloroform: 3:2) to obtain a crude product. Recrystallization was performed twice using methanol to chloroform (volume ratio, 1:2) as a mixed solvent to obtain 90 mg of a reddish brown solid Fu-6. The synthetic route is as follows:
Figure BDA0003290116200000142
the nuclear magnetic detection result of the conjugated organic compound Fu-6 prepared in this example is as follows:
1H NMR(400MHz,CDCl3,ppm)δ:8.41(q,J＝6.8Hz,2H),7.58(t,J＝7.6Hz, 2H),4.62(d,J＝7.6Hz,4H),3.96(q,J＝7.2Hz,8H),2.83(d,J＝7.2Hz,4H), 2.12-1.94(m,4H),1.46(t,J＝6.8Hz,12H),1.19-0.58(m,72H)。
example 8
The embodiment provides a preparation method of an organic solar cell of a conjugated organic compound Fu-4, which comprises the following steps:
8mg of Fu-4 and 8mg of Y6 were mixed, 1mL of chloroform was added to dissolve, an optically active layer was prepared on the ITO glass substrate modified with PEDOT: PSS by spin coating, the active layer was thermally annealed (100 ℃ C./10 min), and then PDINO (concentration: 1.5mg mL) was spin coated-1Ethanol solution of (a) layer, and finally evaporating Al to prepare the cathode.
Performance of the photovoltaic device: at white light 1.5G (100mW cm)-2) Under irradiation, open circuit voltage (V)oc) 0.88V, short-circuit current (J)sc)＝18.8mA cm-2The Fill Factor (FF) is 0.630, and the Photoelectric Conversion Efficiency (PCE) is 10.4%.
Example 9
The embodiment provides a preparation method of an organic solar cell of a conjugated organic compound Fu-6, which comprises the following steps:
mixing 8mg Fu-6 and 6mgY6, adding 1mL chloroform for dissolving, preparing a photoactive layer on the ITO glass substrate modified by ZnO by spin coating, carrying out thermal annealing treatment (100 ℃/10min) on the active layer, and finally respectively evaporating MoO3And an Ag layer to obtain the battery.
Performance of the photovoltaic device: at white light 1.5G (100 mWcm)-2) Under irradiation, open circuit voltage (V)oc) 0.84V, short-circuit current (J)sc)＝19.5mA cm-2The Fill Factor (FF) is 0.610, and the Photoelectric Conversion Efficiency (PCE) is 10.0%.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. A conjugated organic compound is characterized in that the conjugated organic compound takes a cyanoindenopyridine unit as an end group, and the structural formula of the conjugated organic compound is shown as a formula I, wherein the formula I is as follows:
Figure FDA0003290116190000011
wherein Ar is a unit comprising a pi conjugated structure; r1And R2Comprises the same or different hydrogen atoms, straight chain or branched chain alkyl with 2-20 carbon atoms or cycloalkyl with 5-9 carbon atoms; x and Y comprise the same or different H, F, Cl or Br.
2. The conjugated organic compound of claim 1, wherein Ar has a structural formula shown in formula ii, wherein formula ii is:
Figure FDA0003290116190000012
wherein R comprises linear or branched alkyl with 2-20 carbon atoms or linear alkylbenzene with 2-20 carbon atoms.
3. The conjugated organic compound of claim 1, wherein Ar has a structural formula represented by formula three, wherein formula three is:
Figure FDA0003290116190000013
wherein R is3Comprises a linear or branched alkyl with 2-20 carbon atoms or a linear alkylbenzene with 2-20 carbon atoms; r4And R5Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
4. The conjugated organic compound of claim 1, wherein Ar has a structural formula shown as formula IV, wherein formula IV is:
Figure FDA0003290116190000021
wherein R is6Comprises a linear or branched alkyl with 2-20 carbon atoms or a linear alkylbenzene with 2-20 carbon atoms; r7Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
5. The conjugated organic compound of claim 1, wherein Ar has a structural formula as shown in formula five, wherein formula five is:
Figure FDA0003290116190000022
wherein R is8And R9Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r10And R11Comprises the same or different linear or branched alkyl with 2-20 carbon atoms or linear or branched alkoxy with 2-20 carbon atoms.
6. The conjugated organic compound of claim 1, wherein Ar has a structural formula represented by formula six, wherein formula six is:
Figure FDA0003290116190000023
wherein R is12And R13Comprises the same or different linear chain or branched chain alkyl with 2-20 carbon atoms or linear alkyl benzene with 2-20 carbon atoms; r14Including a linear or branched alkyl group having 2 to 20 carbon atoms or a linear or branched alkoxy group having 2 to 20 carbon atoms.
7. A process for the preparation of the conjugated organic compound according to any one of claims 1 to 6, comprising the steps of:
step S1, under the protection of inert gas, dissolving 1 molar equivalent of aldehyde compound and 5-10 times of excessive cyano-indanone derivative in a reaction solvent, dripping 3-5 times of excessive organic amine at room temperature, heating and refluxing for reaction for 12-36h, and obtaining a primary product after the reaction solvent is evaporated to dryness;
and step S2, performing column chromatography separation, drying and recrystallization on the primary product obtained in the step S1 to obtain the conjugated organic compound with the purity of more than 99.5%.
8. A process for the preparation of the conjugated organic compound according to any one of claims 1 to 6, comprising the steps of:
step T1, under the protection of inert gas, dissolving 1 molar equivalent of the compound a in a reaction solvent, dripping organic amine with the excess amount of 3-5 times at room temperature, heating and refluxing for 12-36h, and obtaining an initial product after the reaction solvent is evaporated to dryness;
step T2, carrying out column chromatography separation, drying and recrystallization on the primary product obtained in the step T1 to obtain a conjugated organic compound with the purity of more than 99.5 percent,
the structural formula of the compound a is shown as a formula VII, wherein the formula VII is as follows:
Figure FDA0003290116190000031
wherein Ar is a unit comprising a pi conjugated structure.
9. The method for producing a conjugated organic compound according to claim 7 or 8, wherein the reaction solvent comprises chloroform.
10. Use of a conjugated organic compound according to any one of claims 1 to 6 for the preparation of a photovoltaically functional device, wherein the photovoltaically functional device is an organic solar cell.
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