CN117659053A - Indole diketone condensed ring oligomer with end capping, preparation method and application thereof - Google Patents
Indole diketone condensed ring oligomer with end capping, preparation method and application thereof Download PDFInfo
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- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
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- 239000002904 solvent Substances 0.000 claims description 15
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- 241000252506 Characiformes Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
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- QNLOWBMKUIXCOW-UHFFFAOYSA-N indol-2-one Chemical compound C1=CC=CC2=NC(=O)C=C21 QNLOWBMKUIXCOW-UHFFFAOYSA-N 0.000 description 1
- FGFUBBNNYLNVLJ-UHFFFAOYSA-N indolone Natural products C1=CC=C2C(=O)C=NC2=C1 FGFUBBNNYLNVLJ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to an indole dione condensed ring oligomer with end capping, a preparation method and application thereof. The novel indole diketone condensed ring oligomer is synthesized by a simple and environment-friendly method, has a structure shown in a formula (I), and has the advantages of high synthesis efficiency, simplicity and convenience in operation, low cost and good solubility and absorption energy level. Meanwhile, the oligomer obtained by the method has good plane rigid structure and good accumulation, is favorable for the transmission of electrons between molecules and in molecules, has strong conjugation effect when the maximum absorption wavelength is in a near infrared two region, has excellent organic chemical transistor (OECT) performance and biological synapse simulating function, and has the advantages of high sensitivity, low cost, and the like in the fields of organic chemical transistors (OECT), artificial synapses and the likePotential application prospect.
Description
Technical Field
The invention belongs to the technical field of organic semiconductor materials, and particularly relates to an indole dione condensed ring oligomer with end capping, a preparation method and application thereof.
Background
Organic semiconductor materials have gained wide attention due to their advantages such as good flexibility, ductility, and controllability. Among them, p-type semiconductor materials develop more rapidly, while n-type materials develop more slowly because they are susceptible to water oxygen in the atmospheric environment. Moreover, there are relatively few building blocks with electron deficiency, and synthesis is relatively difficult, which makes n-type materials have a large development space. At present, polymer semiconductors are widely studied, but the synthesis of polymers is complex and subject to batch limitations. Compared with common polymers, the small molecule semiconductor has the advantages of high purity, definite structure, easy synthesis, small batch-to-batch variation and the like, but has poor film forming property and low conjugation effect, so that the small molecule semiconductor is difficult to apply in large-area and large-scale.
Indole dione derivatives are a kind of organic semiconductor materials which are researched very widely recently, and are widely applied to the preparation of small organic molecules and polymer semiconductors as building blocks which are light-resistant and lack electrons. Meanwhile, compared with a commonly used conjugated system with C-C single bonds, the conjugated framework is connected by non-twisted carbon-carbon double bonds, so that the conjugated system has a very rigid plane structure, eliminates the obstacle of rotation torsion to charge transmission, has delocalized front molecular orbits, shows longer lasting length, and has very important application prospect in the direction of an organic semiconductor. Therefore, the synthesis of the indole dione derivative polymer semiconductor with the rigid skeleton has important application value.
Currently, oligomeric semiconductors are gaining attention as compared to polymeric and small molecule semiconductors. The oligomer semiconductor combines the advantages of both polymer and small molecule, not only can obtain a high-purity definite molecular structure, is not affected by batches, but also can ensure better film forming property and conjugation effect, thereby having wide application prospects in the fields of organic electro-chemical transistors (OECTs), organic Field Effect Transistors (OFETs), organic Thermoelectricity (OTEs) and the like.
In conclusion, the development of the novel indoledione oligomer semiconductor material with the rigid framework has important potential application value.
Disclosure of Invention
In order to overcome the defects in the prior art, the primary object of the invention is to provide an indoledione condensed ring oligomer.
The second object of the present invention is to provide a method for producing the above-mentioned indoledione condensed ring oligomer. The synthesis method of the indole diketone condensed ring oligomer is simple, economical and green.
It is a third object of the present invention to provide the use of the above-mentioned indoledione type condensed ring oligomer. The indole diketone condensed ring oligomer has good solubility and lower energy level, has a rigid plane structure, has good accumulation, and is favorable for the transmission of electrons between molecules. In addition, the maximum absorption wavelength of the indole dione small molecular compound is in a near infrared II region, has a strong conjugation effect, and has important potential application prospects in the fields of organic electro-chemical transistors (OECTs), artificial synapses and the like.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an indoledione condensed ring oligomer, which has a structure shown in a formula (I):
in the formula (I),selected from->
Selected from->
Selected from->
R is selected from a straight or branched alkyl chain, a polyethylene glycol chain, and a hybrid chain.
Preferably, the indoledione condensed ring oligomer has a structure represented by formula (ii):
in the formula (II), R is selected from
One or more of the following.
More preferably, the indoledione condensed ring oligomer has a structure represented by formula (1):
in a second aspect, the present invention provides a method for preparing the indoledione condensed ring oligomer according to the first aspect, which is shown in the following reaction scheme, and includes the following steps:
s1, dissolving a terminal group and 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone shown in a formula (III) in an organic solvent, adding a catalyst, performing low-temperature reaction, removing the solvent after the reaction, and purifying by a chromatographic silica gel column to obtain a small molecular compound shown in a formula (V);
s2, dissolving a small molecular compound shown in a formula (V), 3,8- (3-decyl tridecyl) -1,3,6, 8-tetrahydroindole [7,6-g ] indole-2, 7-dione and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a chromatographic silica gel column to obtain the small molecular compound shown in the formula (IV);
s3, dissolving a small molecular compound shown in a formula (IV), 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a silica gel chromatographic column to obtain a compound shown in a formula (II);
in the reaction formula, R has the same value as the formula (II) in the first aspect.
Preferably, the terminal group includes, but is not limited to, 3-ethyl-2-thio-4-thiazolidinedione.
Preferably, the 3, 8-diradical-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone shown in formula (III), the small molecule compound shown in formula (V) and the small molecule compound shown in formula (IV) are respectively selected from the following structural formulas:
preferably, the catalyst of step S1 includes (but is not limited to) triethylamine.
Preferably, the temperature of the low-temperature reaction in the step S1 is ice bath environment (0 ℃) for 1-3 hours.
Preferably, the temperature of the high-temperature reaction in the step S2 is 100-120 ℃ and the time is 0.5-2h; and step S3, the temperature of the high-temperature reaction is 100-120 ℃ and the time is 10-15h.
In a third aspect the invention provides the use of the indoledione condensed ring oligomers of the first aspect in fields including organic electrochemical transistors (OECTs), artificial synapses, organic Thermoelectrics (OTEs), organic Field Effect Transistors (OFETs).
The invention provides a novel conjugated indole dione oligomer which has good solubility and simple and economic green synthetic method, a series of indole dione oligomers with good solubility are prepared by introducing end groups, the oligomer is simple and economic green in method, and the oligomer has excellent performance as an organic semiconductor, has a maximum absorption wavelength in a near infrared II region, has a very strong conjugation effect, shows excellent organic chemical transistor (OECT) performance and biological synaptic function, has potential application prospects in the fields of organic chemical transistors (OECTs), artificial synapses and the like, and is also expected to be applied to the fields of Organic Field Effect Transistors (OFETs), organic Thermoelectricity (OTEs) and the like.
Compared with the prior art, the invention has the beneficial effects that:
compared with a polymer and a small molecule semiconductor, the oligomer semiconductor combines the advantages of the polymer and the small molecule, not only can the determined molecular structure with high purity be obtained, and the oligomer semiconductor is not influenced by batches, but also can ensure better film forming property and conjugation effect. Therefore, the novel indole diketone condensed ring oligomer is synthesized by a very simple method, and the synthesis method is simple, convenient, economical and environment-friendly, and the obtained compound has better solubility (can be dissolved in common solvents such as dichloromethane, chloroform, hexafluoroisopropanol and the like) and lower energy level. Meanwhile, the oligomer obtained by the method has a good plane rigid structure, good accumulation, is favorable for the transmission of electrons in molecules and among molecules, has a strong conjugation effect in a near infrared II region, shows excellent organic electrochemical transistor (OECT) performance, can simulate biological synapses, can be used for preparing artificial synapses, has potential application prospects in the fields of organic electrochemical transistors (OECTs), artificial synapses and the like, and is expected to be applied to the fields of Organic Field Effect Transistors (OFETs), organic Thermoelectricity (OTEs) and the like.
Drawings
FIG. 1 shows an indole dione condensed ring oligomer (1) 1 H NMR map;
FIG. 2 is a mass spectrum of the indoledione condensed ring oligomer (1);
FIG. 3 is a CV diagram of an indoledione condensed ring oligomer (1);
FIG. 4 is an ultraviolet absorbance graph of the indoledione fused ring oligomer (1);
FIG. 5 is a graph of the mechanochemical transistor transfer profile of an indoledione fused ring oligomer (1);
FIG. 6 is a graph of the current-voltage transfer characteristics of an artificial synapse device for an indolone condensed ring oligomer (1);
FIG. 7 is a Spike Voltage dependent plasticity (STDP) behavior of an indole dione fused ring oligomer (1).
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, are conventional, and the experimental materials used in the following examples, unless otherwise specified, are commercially available.
The invention provides an indole diketone condensed ring oligomer, which has a structure shown in a formula (I):
in the formula (I),selected from->
Selected from->
Selected from->R is selected from a straight or branched alkyl chain, a polyethylene glycol chain, and a hybrid chain.
Preferably, the indoledione condensed ring oligomer has a structure represented by formula (ii):
in the formula (II), R is selected from
One or more of the following.
The preparation method of the indole dione condensed ring oligomer shown in the formula (II) comprises the following steps:
(1) Dissolving a terminal group and 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone shown in a formula (III) in an organic solvent, adding a catalyst, performing low-temperature reaction, removing the solvent after the reaction, and purifying by a chromatographic silica gel column to obtain a small molecular compound shown in a formula (V); such terminal groups include, but are not limited to, 3-ethyl-2-thio-4-thiazolidinedione.
(2) Dissolving a small molecular compound shown in a formula (V), 3,8- (3-decyl tridecyl) -1,3,6, 8-tetrahydroindole [7,6-g ] indole-2, 7-dione and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a chromatographic silica gel column to obtain the small molecular compound shown in the formula (IV);
(3) Dissolving a small molecular compound shown in a formula (IV), 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a silica gel chromatographic column to obtain the compound shown in the formula (II).
The preparation method of the indole dione condensed ring oligomer is further described below with specific examples, and it should be noted that this is only a preferred example of the present invention, and it is understood by those skilled in the art that the present invention is not limited to these examples.
Example 1 an indole dione fused ring oligomer [ Compound (1) ] and a method for producing the same
The synthesis of the indoledione oligomer of formula (1) comprises the following steps according to the following reaction scheme:
(1) 300.0mg of compound 1 (1 equivalent), 75.0mg of 3-ethyl-2-thio-4-thiazolidinedione (1 equivalent) was charged into a microwave tube, 0.1mL of triethylamine and 30mL of ultra-dry chloroform were further added, reacted at 0℃in an ice bath environment for 1 hour, and after the reaction, the solvent in the system was rotationally evaporated and purified by a silica gel column (eluent: dichloromethane/methanol=100/2) to give compound 2. Wherein, compound 1 is prepared by the method described in the following documents:
Highly Efficient Mixed Conduction in N-type Fused Small Molecule Semiconductors[J].Adv.Funct.Mater.2022,2203937。
(2) 50.0mg of Compound 2 (1 eq), 56.0mg of 3,8- (3-decyltridecyl) -1,3,6, 8-tetrahydroindole [7,6-g ] indole-2, 7-dione (1 eq) and 2mg of PTSA (p-toluenesulfonic acid, (0.3 eq)) were added to a microwave tube, 10mL of ultra-dry toluene was added, reacted at 110℃for 0.5h, the solvent in the system was rotationally evaporated after the reaction, and the compound 3 was purified by a silica gel column.
(3) 30mg of Compound 3 (2 eq), 6mg of Compound 1 (1 eq) and 1mg of PTSA (p-toluenesulfonic acid, 0.3 eq)) were added to a microwave tube, 4mL of ultra-dry toluene was added, the reaction was carried out at 110℃for 12 hours, the solvent in the system was rotationally evaporated after the reaction, and the product compound (1) was obtained by purification by a silica gel column.
(4) Detection of the product by means of a AVANCE III M liquid Nuclear magnetic resonance spectrometer manufactured by Bruker, switzerland 1 H NMR with deuterated-1, 2-tetrachloroethane (TCE-D) 2 ) The internal standard is Tetramethylsilane (TMS). Mass spectrometry was performed using an AB Sciex-5800 MALDI-TOF mass spectrometer and a Bruker Solarix XR mass spectrometer.
The compound (1) 1 The H NMR chart and the mass spectrum chart are shown in FIG. 1 and FIG. 2 respectively, and nuclear magnetic resonance data are as follows:
1 H NMR(500MHz,TCE-D 2 ,393K),δ(ppm):9.05(m,10H),8.14(d,2H),7.97(m,4H),7.82(m,4H),4.59(m,12H),4.39(m,8H),4.29(m,4H),4.01(m,12H),3.56-3.77(m,60H),3.50(m,12H),3.34(m,18H),1.91(m,8H),1.64(m,4H),0.90(m,30H)。
experimental example 1 characterization and Performance test of indoledione condensed Ring oligomers
1. Test method
(1) The Cyclic Voltammetry (CV) test was performed on a standard commercial electrochemical analyzer (Shanghai Chen Hua instruments Co., ltd., CHI 520E), first washing 1X 1cm ITO glass with soapy water, deionized water in order, and then spin-coating hexafluoroisopropanol solution (10 mg/mL) containing the oligomer (the indole dione fused ring oligomer of example 1) onto the ITO glass sheet, using 0.1M sodium chloride solution as electrolyte, the three electrode system consisted of ITO glass sheet working electrode, platinum wire counter electrode and Ag/AgCl reference electrode, the potential of which was calibrated internally based on ferrocene.
(2) First, 1X 1cm soda lime glass was washed with soapy water and deionized water in this order, then hexafluoroisopropanol solution (10 mg/mL) containing the oligomer (the indoledione type condensed ring oligomer of example 1) was spin-coated on a glass sheet, and then the ultraviolet absorption spectrum of the oligomer film was measured by using a Shimadzu UV-3600 type ultraviolet-visible spectrophotometer.
(3) A quartz cuvette of 1X 1cm is used as a sample cell, and an electrochemical test is carried out by using a CHI620E electrochemical analyzer of Shanghai Chen Hua instruments Co. OECT is fabricated by cleaning the substrate with a piranha solution, then drying with a nitrogen gun, and evaporating gold heat onto the glass substrate and patterning by standard photolithography/lift-off processes. Hexafluoroisopropanol solution (10 mg/mL) containing oligomers (the indoledione condensed ring oligomers of example 1) was spin coated to form an active channel layer (the oligomers of example 1 were soluble in common solvents such as methylene chloride, chloroform, hexafluoroisopropanol, etc.), the electrolyte and gate electrode were 0.1m NaCl aqueous solution and Ag/AgCl particles, respectively, a small Polydimethylsiloxane (PDMS) was used to confine the electrolyte, and finally a semiconductor parametric analyzer (Keystight B1500A) and an electrical probe station were used to characterize the device in air at room temperature.
(4) And thermally evaporating chromium and gold on the soda lime glass through a mask plate to obtain the three-terminal electrode transistor with the designed specification and size. An active channel layer was prepared by spin coating a hexafluoroisopropanol solution (10 mg/mL) containing the oligomer (the indoledione condensed ring oligomer of example 1) (the oligomer of example 1 was soluble in common solvents such as methylene chloride, chloroform, hexafluoroisopropanol, etc.). Meanwhile, a sodium chloride gel was used as an electrolyte (4 g of 20wt% gelatin was dissolved in 16mL of deionized water and heated at 60 ℃ until it became a transparent solution, then the solution was cast into a mold and frozen at 4 ℃ for 1 hour to obtain a hydrogel, and the prepared hydrogel was immersed in 0.2M NaCl solution containing 60% v/v glycerol at room temperature (26±2 ℃) for 3 hours to prepare an ionic gel electrolyte), which was covered in a region spanning the organic semiconductor film and gate electrode. Finally, a semiconductor parameter analyzer (Keithley 2612B) is used to apply voltage stimulus to the gate electrode, and a response current, namely a post-synaptic current of the biological synapse, can be obtained at the channel and the source drain, wherein the gate electrode is similar to the front end of the biological synapse, and the channel and the source drain are similar to the rear end of the biological synapse, so that the simulation of the artificial synapse is realized.
2. Test results
(1) The detection results of ultraviolet absorption and cyclic voltammogram test of the indole dione fused ring oligomer [ compound (1) ] of example 1 are shown in fig. 3 to 4.
As can be seen from fig. 3, the LUMO levels of the compound (1) are all around-4.0 eV; as can be seen from FIG. 4, the maximum wavelength of ultraviolet absorption of the compound (1) is about 1000nm, which is favorable for the transmission of electrons in molecules and among molecules.
(2) The test results of the performance of the organic electrochemical transistor (OECT) on the compound (1) are shown in FIG. 5.
As can be seen from fig. 5, the maximum current of the compound (1) reaches 0.14mA, the maximum transconductance reaches 1.2mS, and the organic electrochemical transistor (OECT) performance is excellent.
(3) The artificial synapse device prepared by the compound (1) is subjected to a direct current I-V test, and as can be seen from FIG. 6, the current of the device follows the characteristics of space charge limiting current. Furthermore, it can be seen that the transition between short-range plasticity and long-range plasticity can be achieved by adjusting the pulse voltage.
As can be seen from fig. 7, the post-synaptic current of the artificial synapse device returns to its original state after the stimulation pulse is applied, and the device self-recovery process is similar to the short-range plasticity of the nerve synapse in the organism, thus indicating that the artificial synapse device of compound (1) has the function of simulating the biological synapse.
In conclusion, the indole diketone condensed ring oligomer has good solubility and lower energy level, has a rigid planar structure, has good accumulation and is beneficial to the transmission of electrons among molecules. In addition, the maximum absorption wavelength of the indole dione small molecular compound is in a near infrared II region, has a very strong conjugation effect, shows excellent organic electro-chemical transistor (OECT) performance, can simulate biological synapses, can be used for preparing artificial synapse devices, has potential application prospects in the fields of organic electro-chemical transistors (OECTs), artificial synapses and the like, and is also expected to be applied to the fields of Organic Field Effect Transistors (OFETs), organic Thermoelectric (OTEs) and the like, so that the indole dione small molecular compound has important potential application value.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (10)
1. An indoledione condensed ring oligomer, characterized in that the oligomer has a structure represented by formula (i):
in the formula (I),selected from->
Selected from->
Selected from->
R is selected from a straight or branched alkyl chain, a polyethylene glycol chain, and a hybrid chain.
2. The indoledione fused ring oligomer of claim 1, wherein the oligomer has the structure of formula (ii):
in the formula (II), R is selected from One or more of the following.
3. The indoledione fused ring oligomer of claim 2, wherein the oligomer has the structure of formula (1):
4. the method for producing an indole dione fused ring oligomer according to claim 2, wherein the method comprises the following steps, as shown in the following reaction scheme:
s1, dissolving a terminal group and 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone shown in a formula (III) in an organic solvent, adding a catalyst, performing low-temperature reaction, removing the solvent after the reaction, and purifying by a chromatographic silica gel column to obtain a small molecular compound shown in a formula (V);
s2, dissolving a small molecular compound shown in a formula (V), 3,8- (3-decyl tridecyl) -1,3,6, 8-tetrahydroindole [7,6-g ] indole-2, 7-dione and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a chromatographic silica gel column to obtain the small molecular compound shown in the formula (IV);
s3, dissolving a small molecular compound shown in a formula (IV), 3, 8-di-R-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone and p-toluenesulfonic acid in an organic solvent, removing the solvent after high-temperature reaction, and purifying by a silica gel chromatographic column to obtain a compound shown in a formula (II);
in the reaction formula, R has the same value as in claim 2.
5. The method for preparing an indole dione fused ring oligomer according to claim 4, wherein the terminal group comprises 3-ethyl-2-thio-4-thiazolidinedione.
6. The method for producing an indole dione fused ring oligomer according to claim 4, wherein the 3, 8-diradical-3, 8-indoline [7,6-g ] indole-1, 2,6, 7-tetraketone represented by the formula (III), the small molecule compound represented by the formula (V) and the small molecule compound represented by the formula (IV) are each selected from the following structural formulae:
7. the method for preparing an indole dione fused ring oligomer according to claim 4, wherein the catalyst in step S1 comprises triethylamine.
8. The method for preparing an indole dione condensed ring oligomer according to claim 4, wherein the low temperature reaction in step S1 is performed in an ice bath environment for 1-3 hours.
9. The method for preparing an indole dione condensed ring oligomer according to claim 4, wherein the high temperature reaction in step S2 is performed at 100-120 ℃ for 0.5-2 hours; and step S3, the temperature of the high-temperature reaction is 100-120 ℃ and the time is 10-15h.
10. Use of an indole dione fused ring oligomer according to any one of claims 1 to 3, wherein the field of use comprises an electromechanical chemotransistor, an artificial synapse, an organic thermoelectric, an organic field effect transistor.
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