CN110698476A - Based on C3Symmetrical n-type organic semiconductor material and synthesis and application thereof - Google Patents

Based on C3Symmetrical n-type organic semiconductor material and synthesis and application thereof Download PDF

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CN110698476A
CN110698476A CN201810750393.6A CN201810750393A CN110698476A CN 110698476 A CN110698476 A CN 110698476A CN 201810750393 A CN201810750393 A CN 201810750393A CN 110698476 A CN110698476 A CN 110698476A
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张磊
陈燕
李小楠
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • 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
    • 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

Abstract

The invention discloses a C-based catalyst3Symmetrical n-type organic semiconductor material and synthesis and application thereof. The organic semiconductor material has a structure shown in formula 1, and is prepared by taking a six-membered ring as a parent nucleus and C3Perylene bisimide polycyclic aromatic hydrocarbon which is symmetrically extended outwards. Wherein R is selected from: c2‑60Alkyl, C containing substituents2‑60Alkyl radical, C1‑60Alkoxy, C containing substituents1‑60Alkoxy, aryl containing substituent, alkyl aryl containing substituent, alkyl heteroaryl containing substituent, alkyl heterocyclic radical and alkyl heterocyclic radical containing substituent. In addition, the invention synthesizes the compound with Yamamoto-type coupling reaction design for the first time, and the compound has an almost plane structureThe method is favorable for the transmission of electrons, and provides a molecular model for the electronic structure and the aggregation state of the two-dimensional structure material and the performance of the organic semiconductor.

Description

Based on C3Symmetrical n-type organic semiconductor material and synthesis and application thereof
Technical Field
The invention relates to the technical field of organic materials. More particularly, to a C-based3Symmetrical n-type organic semiconductor material and synthesis and application thereof.
Background
Solar energy is the safest, greenest and most ideal renewable clean energy source for human beings. The organic photovoltaic cell utilizes organic photovoltaic materials to prepare devices to realize photoelectric conversion, can be prepared into flexible large-area devices through a solution processing technology, and has the advantages of light weight, low cost, convenience and the like. The organic photovoltaic cell belongs to the international leading-edge cross research field and has wide application prospect.
Organic solar cells have been developed rapidly over the last decade. Bulk heterojunction solar cells are the focus of research in the current scientific research field, and active layers composed of donor and acceptor are the most important parts of the design, synthesis and performance research cells of high-performance non-fullerene acceptor based on imide materials of such solar cells. Donors develop relatively quickly, while acceptors develop relatively slowly. Originally, the acceptor was mainly fullerene, but the defects of expensive production cost, difficult chemical modification and the like lead the research focus to move to a non-fullerene acceptor which has strong absorption, electronic characteristics and energy level in the visible region and the near infrared region, is easy to adjust and has good matching capability with a donor material. Initially, non-fullerenes developed more slowly with conversion efficiencies of only about 1-3%. Non-fullerene receptors have evolved dramatically since 2014. And in recent years the efficiency has broken through 12%, and has surpassed the fullerene solar cell. In view of the foregoing, the development of novel non-fullerene receptors is the focus of current research.
Imide-based molecules generally have excellent photo, thermal and chemical stability. Meanwhile, the conjugated large pi system in the compound endows the compound with stronger fluorescence performance and photoelectric performance, so that the compound is widely applied to the fields of organic field effect transistors, organic solar cells, photoconductors, electroluminescence, self-assembly, biological fluorescent probes and the like as a photoelectric material. Particularly, in recent years, with the development of organic electronics, perylene imide compounds have been widely paid attention to academic and industrial fields due to their high electron transport efficiency and photoelectric conversion efficiency as one of the most important n-type semiconductors
Disclosure of Invention
Based on the background technologyThe invention provides a method based on C3Symmetrical n-type organic semiconductor material and synthesis and application thereof. The organic semiconductor material of the invention has the structure that six-membered ring is taken as a mother nucleus, C3Perylene bisimide polycyclic aromatic hydrocarbon which is symmetrically extended outwards. The invention synthesizes the organic semiconductor material by Yamamoto-type coupling reaction for the first time.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a C-based3The symmetrical n-type organic semiconductor material has the following structure:
Figure BDA0001725400900000021
wherein R is selected from: c2-60Alkyl, C containing substituents2-60Alkyl radical, C1-60Alkoxy, C containing substituents1-60Alkoxy, aryl containing substituent, alkyl aryl containing substituent, alkyl heteroaryl containing substituent, alkyl heterocyclic radical and alkyl heterocyclic radical containing substituent.
Preferably, said C containing a substituent2-60Substituents in the alkyl group are selected from: at least one of a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group;
said C containing a substituent1-60The substituent of the alkoxy, the aryl containing the substituent, the alkyl heteroaryl containing the substituent and the alkyl heterocyclic radical containing the substituent is selected from the following groups: at least one of a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group, and a hydrazino group.
Preferably, the alkoxy group is selected from: any one of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and eicosyloxy.
Preferably, the aromatic group is selected from: at least one of phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pentacenyl, trianilino, pyrenyl, indenyl, biphenyl, and fluorenyl.
Preferably, the heterocyclic group and the heteroaromatic group are both selected from: thiophene, benzothiophene, pyran, benzopyran, furan, benzofuran, imidazole, benzimidazole, pyrazole, benzopyrazole, pyrrole, benzopyrrole, pyridine, benzopyridine, pyrazine, benzopyrazine, indole, isoindole, benzindole, pyrimidine, benzopyrimidine, naphthyridine, benzonaphthyridine, pyridazine, benzopyridazine, indazole, benzindazole, purine, benzopyrurine, quinolizine, any of benzoquinolizine, quinoline, benzoquinoline, indolizine, benzaindolizine, phthalazine, benzophthalazine, quinoxaline, benzoquinoxaline, thiazole, benzothiazole, carboline, benzocarbazine, phenanthridine, benzophenanthridine, phenanthroline, benzophenanthroline, acridine, benzacridine, phenazine, benzophenazine, phenothiazine, carbazole, benzocarbazole, dithienopyrrole, tertiothiophene, tetrathiothiophene, and pentathiothiophene.
Preferably, R is selected from C2-60Alkyl, C containing substituents2-60An alkyl group;
the substituents are selected from: at least one of a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group.
More preferably, R is
Figure BDA0001725400900000031
The R is2、R3Is selected from C3-12Alkyl radical, R2、R3The same or different. Preferably, R2、R3Is selected from C5-12An alkyl group.
More preferably, R is
Figure BDA0001725400900000032
The invention also provides a synthesis method of the organic semiconductor material, which comprises the following steps: the compound of the formula 2 is subjected to Yamamoto-type coupling reaction (Yamamoto-type coupling reaction) to obtain a compound of a formula 1;
Figure BDA0001725400900000033
preferably, the conditions of the yamamoto coupling reaction include: bis- (1, 5-cyclooctadiene) nickel as a catalyst; 1, 5-cyclooctadiene as a reducing agent; bipyridine as a ligand; tetrahydrofuran is used as a solvent.
Preferably, the specific process of the yamamoto coupling reaction comprises:
adding 1, 5-cyclooctadiene and bipyridine into tetrahydrofuran solvent, and adding bis- (1, 5-cyclooctadiene) nickel under anaerobic condition;
slowly adding the compound shown in the formula 2 into a system for reaction;
after the reaction is finished, purifying to obtain the compound shown in the formula 1.
Preferably, the compound of formula 2 is dissolved in tetrahydrofuran and slowly added into the system for reaction.
Preferably, the temperature of the reaction is 70 ℃.
Preferably, the equivalent ratio of 1, 5-cyclooctadiene, bipyridine, bis- (1, 5-cyclooctadiene) nickel and the compound of formula 2 is 2:1.25:1.25: 1.
Preferably, the oxygen-free condition is achieved by nitrogen or inert gas shielding.
Preferably, the purification is silica gel column chromatography, and the eluent is chloroform: methanol is 100: 1.
Preferably, the compound of formula 2 is prepared by the following steps:
carrying out bromination reaction on naphthalene hexacyclic to obtain a compound shown in a formula 3;
carrying out boron esterification reaction on the compound shown in the formula 3 and a boronizing reagent to obtain a compound shown in a formula 4;
reacting the compound shown in the formula 4 with 4-bromo-1, 8-naphthalic anhydride to obtain a compound shown in a formula 5;
carrying out a ring closure reaction on the compound of the formula 5 under the action of Lewis acid to obtain a compound of a formula 6;
compounds of formula 6 with R-NH2Reacting to form the corresponding compound of formula 7;
brominating the compound of formula 7 to obtain a compound of formula 2;
Figure BDA0001725400900000041
preferably, the bromination reaction of the naphthalene hexacyclic compound and N-bromosuccinimide is carried out in an N, N-dimethylformamide solvent to obtain the compound of formula 3.
Preferably, the boronizing agent is bis (pinacolato) diboron, and the boron esterification reaction is carried out under the action of a catalyst 1,1' -bis-diphenylphosphino ferrocene palladium dichloride and potassium acetate.
Preferably, the compound of formula 4 is reacted with 4-bromo-1, 8-naphthalic anhydride in the presence of a catalyst of tetrakis (triphenylphosphine) palladium to give the compound of formula 5.
Preferably, the lewis acid in the ring closure reaction is aluminum trichloride.
In another aspect, the present invention provides the use of the above organic semiconductor material in an organic optoelectronic device.
The invention has the following beneficial effects:
the invention designs and synthesizes a C-type copolymer which takes a six-membered ring as a mother nucleus by using Yamamoto-type coupling reaction for the first time3Perylene bisimide polycyclic aromatic hydrocarbon which is symmetrically extended outwards. The compound has an almost plane structure, and is beneficial to the transmission of electrons; provides a molecular model for the electronic structure, the aggregation state and the performance of the organic semiconductor of the two-dimensional structural material.
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The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 is a synthetic route diagram of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
FIG. 1 shows a synthetic route diagram according to the present invention. The invention designs a simple synthesis method, Yamamoto-type ligation reaction, and prepares a novel molecule, wherein six-membered ring is used as a parent nucleus, C3Perylene bisimide polycyclic aromatic hydrocarbon which is symmetrically extended outwards. The method solves the problems of low yield and the like in the existing organic synthesis to a certain extent, and ensures the feasibility in the experimental process.
Synthesis of Compound 2:
a250 mL two-necked flask was charged with 10g (64.8mmol,1eq) of 1-naphthalene-hexacyclic followed by 50mL of N, N-dimethylformamide. 11.5g (64.8mmol,1eq) of N-bromosuccinimide were weighed out and dissolved in 50mL of N, N-dimethylformamide, and added to a 100mL constant pressure dropping funnel with aeration of the gas for N2Atmosphere protection, then slowly dropwise adding the solution of the N-bromosuccinimide into the reaction system for about 1h, and then after continuously stirring at room temperature for 3h, carrying out post-treatment: the organic layer was washed twice with water, once with saturated brine, and then dried over anhydrous sodium sulfate, filtered, and spin-dried. Purifying with silica gel column, and eluting with petroleum ether. The product was obtained as a green solid, 2, 13.9g, yield: 92 percent.
1H NMR(400MHz,Chloroform-d)δ＝7.76(d,J＝8.4Hz,1H),7.65(d,J＝7.3Hz,1H),7.54(s,1H),7.32(d,J＝6.8Hz,1H),7.12(d,J＝7.3Hz,1H),3.40(m,2H),3.37-3.29(m,2H).
Synthesis of Compound 3:
a250 mL two-necked flask was weighed with 4g (17mmol,1eq)2, 6.6g (25.7mmol,1.5eq) bis (pinacolato) diboron, and 0.63g(0.86mmol,0.05eq)1,1' -bisdiphenylphosphinoferrocene palladium dichloride and 5g (51.5mmol,3eq) potassium acetate were added, followed by 80mL of dimethyl sulfoxide. After inflation and ventilation, N is carried out2And (3) protecting the atmosphere, adding the mixture into an oil bath at the temperature of 100 ℃ for reflux stirring for 3 hours, stopping the reaction, and performing after-treatment after the reaction system is cooled to room temperature. After extraction with water and dichloromethane, the organic layer was washed twice with water and once with saturated brine, the organic layer was dried over anhydrous sodium sulfate, filtered and spin-dried. Silica gel column purification, petroleum ether: dichloromethane ═ 3: 1 as eluent. The product was obtained as a yellow solid, 3, 4.8g, yield: 76 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.37(d,J＝8.4Hz,1H),7.64-7.44(m,1H),7.28(d,J＝6.5Hz,2H),3.39(s,4H),1.41(s,12H).
Synthesis of Compound 4:
a250 mL two-necked flask was charged with 1.8g (6.42mmol,1eq) of 3, 2.14g (7.7mmol,1.2eq) of 4-bromo-1, 8-naphthalic anhydride and 0.37g (0.32mmol,0.05eq) of tetrakis (triphenylphosphine) palladium, 90mL of toluene, 18mL of 2M potassium carbonate, and 6mL of ethanol, and then purged with N2The atmosphere was blanketed and then added to a 100 ℃ oil bath with stirring at reflux overnight. After the reaction is terminated, the reaction system is cooled to room temperature, and then is filtered by suction, so that a white solid product 4, 0.9g, yield: 40 percent. And directly feeding the mixture to the next experiment.
Synthesis of Compound 5:
a100 mL two-necked flask was charged with air and charged with N.sub.g by weighing 0.6g (1.7mmol,1eq)4 and 2.3g (17mmol,10eq) of anhydrous aluminum trichloride and adding 15mL of chlorobenzene super-dry solvent2The atmosphere was blanketed and then transferred to an oil bath at 145 ℃ and stirred at reflux overnight. After the reaction is stopped, cooling the reaction system to room temperature, extracting with dilute hydrochloric acid and chloroform, spin-drying, heat treating with methanol, and performing suction filtration while hot to obtain a red solid product 5, 0.53g, yield: 90 percent. Directly feeding the mixture to the next reaction.
Synthesis of compound 6 a:
a100 mL two-necked flask was charged with 0.5g (1.44mmol,1eq) of 5 and 1.3g (4.3mmol,3eq) of 6-aminoundecane, followed by 30mL of N, N-dimethylAnd (3) a formamide. After performing charging and ventilation N2And (3) protecting the atmosphere, adding the mixture into an oil bath at the temperature of 100 ℃, refluxing and stirring for 2 hours, removing the reaction device, extracting the mixture by using trichloromethane and water after the temperature is reduced to room temperature, washing the organic layer twice by using water, washing the organic layer once by using saturated salt, drying the organic layer by using anhydrous sodium sulfate, filtering, spinning, and purifying by using a silica gel column. Using petroleum ether: and (4) preparing eluent by using dichloromethane as 1: 2. The product 6a was obtained as a red solid, 0.34g, yield: 48 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.50(m,2H),8.21(d,J＝7.6Hz,2H),8.17(d,J＝8.1Hz,2H),7.37(d,J＝7.5Hz,2H),5.21(m,1H),3.43(s,4H),2.31(m,2H),2.25(m,2H),1.22(m,12H),0.85(m,6H).
Synthesis of compound 6 b:
a100 mL two-necked flask was weighed with 0.5g (1.44mmol,1eq) of 5 and 1.27g (4.3mmol,3eq) of 2-octyldodecylamine, followed by 30mL of N, N-dimethylformamide. After performing charging and ventilation N2And (3) protecting the atmosphere, adding the mixture into an oil bath at the temperature of 100 ℃, refluxing and stirring for 2 hours, removing the reaction device, extracting the mixture by using trichloromethane and water after the temperature is reduced to room temperature, washing the organic layer twice by using water, washing the organic layer once by using saturated salt, drying the organic layer by using anhydrous sodium sulfate, filtering, spinning, and purifying by using a silica gel column. Using petroleum ether: and (4) preparing eluent by using dichloromethane as 1: 2. The product 6b was obtained as a red solid, 0.41g, yield: 45 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.44(d,J＝8.0Hz,2H),8.18(d,J＝7.6Hz,2H),8.13(d,J＝8.1Hz,2H),7.37(d,J＝7.5Hz,2H),4.12(d,J＝7.3Hz,2H),3.42(s,4H),2.05(s,1H),1.22(m,32H),0.90(m,6H).
Synthesis of compound 6 c:
a100 mL two-necked flask was charged with 0.5g (1.44mmol,1eq) of 5 and 1.3g (4.3mmol,3eq) of 2-decyltetradecylamine, followed by 30mL of N, N-dimethylformamide. After performing charging and ventilation N2Atmosphere protecting, adding into 100 deg.C oil bath, reflux stirring for 2 hr, removing reaction device, cooling to room temperature, extracting with chloroform and water, washing the organic layer with water twice, washing with saturated salt water once, and washing the organic layer with anhydrous sulfuric acidSodium drying, filtering, spin drying, silica gel column purification. Using petroleum ether: and (4) preparing eluent by using dichloromethane as 1: 2. The product 6c was obtained as a red solid, 0.4g, yield: 45 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.43(d,J＝8.0Hz,2H),8.17(d,J＝7.6Hz,2H),8.12(d,J＝8.1Hz,2H),7.36(d,J＝7.5Hz,2H),4.12(d,J＝7.3Hz,2H),3.43(s,4H),2.01(s,1H),1.22(m,40H),0.85(m,6H).
The R groups in product 6 above are:
Figure BDA0001725400900000071
from the above synthesis of compounds 6a, 6b and 6c, it is only necessary to change the amine in this step to obtain compounds 6 with different R groups, which, according to tests, can be other common alkyl, alkoxy, aryl, heterocyclic and the like groups in addition to the R groups listed above. The invention is not further illustrated here.
Synthesis of compound 7 a:
a100 mL two-necked flask was charged with 0.43g (0.86mmol,1eq) of 6a, 0.6g (3.44mmol,4eq) of N-bromosuccinimide, and 0.07g (0.215mmol,0.25eq) of benzoyl peroxide, followed by 25mL of chloroform. Charging and ventilating N2The organic layer is washed twice with water, washed once with saturated salt solution, dried with anhydrous sodium sulfate, filtered, dried by spinning, and purified by silica gel column. Using petroleum ether: dichloromethane ═ 1:2 as eluent gave the product 7a as a red solid, 0.25g, yield: 45 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.57(m,2H),8.31(d,J＝8Hz,2H),8.00(d,J＝4Hz,2H),7.41(d,J＝7.5Hz,2H),5.21(m,1H),2.29(m,2H),1.90(m,2H),1.43-1.01(m,32H),0.9(t,J＝4Hz,6H).
Synthesis of compound 7 b:
a100 mL two-necked flask was charged with 0.53g (0.86mmol,1eq) of 6b, 0.6g (3.44mmol,4eq) of N-bromosuccinimide, and 0.07g (0.215mmol,0.25eq) of benzoyl peroxide, followed by 25mL of chloroform. Charging and ventilating N2Atmosphere surrounding protection, reflux stirringStirring for 2 hr, extracting with chloroform and water, washing the organic layer twice with water, washing with saturated salt solution once, drying the organic layer with anhydrous sodium sulfate, filtering, spin drying, and purifying with silica gel column. Using petroleum ether: dichloromethane ═ 1:2 as eluent gave the product 7b as a red solid, 0.29g, yield: 44 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.47(d,J＝7.9Hz,2H),8.23(d,J＝8Hz,2H),7.96(d,J＝4Hz,2H),7.42(d,J＝7.5Hz,2H),4.10(d,J＝7.3Hz,2H),1.99(s,1H),1.43-1.01(m,32H),0.86(t,J＝4Hz,6H).
Synthesis of compound 7 c:
a100 mL two-necked flask was charged with 0.54g (0.86mmol,1eq) of 6c, 0.6g (3.44mmol,4eq) of N-bromosuccinimide, and 0.07g (0.215mmol,0.25eq) of benzoyl peroxide, followed by 25mL of chloroform. Charging and ventilating N2The organic layer is washed twice with water, washed once with saturated salt solution, dried with anhydrous sodium sulfate, filtered, dried by spinning, and purified by silica gel column. Using petroleum ether: dichloromethane ═ 1:2 as eluent gave the product 7c as a red solid, 0.3g, yield: 45 percent.
1H NMR(400MHz,Chloroform-d)δ＝8.53(d,J＝7.9Hz,2H),8.34(d,J＝8Hz,2H),8.08(d,J＝4Hz,2H),7.52(d,J＝7.5Hz,2H),4.11(d,J＝7.3Hz,2H),2.00(s,1H),1.43-1.01(m,40H),0.84(t,J＝4Hz,6H).
Synthesis of compound 8 a:
a100 mL two-necked flask was charged with 0.08g (0.7mmol,2eq) of 1, 5-cyclooctadiene, 0.07g (0.45mmol,1.25eq) of bipyridine and 10mL of dry tetrahydrofuran, and charged with gas N2After the atmosphere was blanketed, 0.12g (0.45mmol,1.25eq) of bis- (1, 5-cyclooctadiene) nickel was further added, and then 0.23g (0.357mmol,1eq) of 7a was dissolved in 10mL of tetrahydrofuran and slowly added dropwise to the reaction system. The mixture was transferred to an oil bath at 70 ℃ and stirred overnight with heating. And (4) removing the reaction system after the reaction is completely carried out, and evaporating tetrahydrofuran in the reaction system to dryness after the reaction system is cooled to room temperature. Silica gel column purification with chloroform: methanol is 100:1 as eluent. The product was obtained as a blue-violet color 8a, 0.10g, yield：55％。MS(MALDI-TOF):cacld for M-,1492.71；found,1492.71.
Synthesis of compound 8 b:
a100 mL two-necked flask was charged with 0.08g (0.7mmol,2eq) of 1, 5-cyclooctadiene, 0.07g (0.45mmol,1.25eq) of bipyridine and 10mL of dry tetrahydrofuran, and charged with gas N2After the atmosphere was blanketed, 0.12g (0.45mmol,1.25eq) of bis- (1, 5-cyclooctadiene) nickel was further added, and then 0.28g (0.357mmol,1eq) of 7b was dissolved in 10mL of tetrahydrofuran and slowly added dropwise to the reaction system. The mixture was transferred to an oil bath at 70 ℃ and stirred overnight with heating. And (4) removing the reaction system after the reaction is completely carried out, and evaporating tetrahydrofuran in the reaction system to dryness after the reaction system is cooled to room temperature. Silica gel column purification with chloroform: methanol is 100:1 as eluent. The product 8b was obtained as a blue-violet color, 0.11g, yield: 58 percent. MS (MALDI-TOF) cacld for M-,1871.13；found,1871.13.
Synthesis of compound 8 c:
a100 mL two-necked flask was charged with 0.08g (0.7mmol,2eq) of 1, 5-cyclooctadiene, 0.07g (0.45mmol,1.25eq) of bipyridine and 10mL of dry tetrahydrofuran, and charged with gas N2After the atmosphere was blanketed, 0.12g (0.45mmol,1.25eq) of bis- (1, 5-cyclooctadiene) nickel was further added, and then 0.3g (0.357mmol,1eq) of 7c was dissolved in 10mL of tetrahydrofuran and slowly added dropwise to the reaction system. The mixture was transferred to an oil bath at 70 ℃ and stirred overnight with heating. And (4) removing the reaction system after the reaction is completely carried out, and evaporating tetrahydrofuran in the reaction system to dryness after the reaction system is cooled to room temperature. Silica gel column purification with chloroform: methanol is 100:1 as eluent. The product was obtained as a blue-violet color 8c, 0.13g, yield: 59 percent. MS (MALDI-TOF) cacld for M-,2039.32；found,2039.32.
The R group in the product 8 obtained here is determined by the amine in the synthesis process of the compound 6, and corresponding to the R group in the compound 6 and the compound 8, other common alkyl, alkoxy, aryl, heterocycle and the like can be correspondingly adopted. The invention is not further enumerated here. The person skilled in the art can synthesize compounds 8 of the different R groups listed in the description by the above experimental procedures entirely according to the above synthetic steps in combination with the synthetic route of fig. 1.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (10)

1. Based on C3The symmetrical n-type organic semiconductor material is characterized in that the structure is shown as formula 1:
wherein R is selected from: c2-60Alkyl, C containing substituents2-60Alkyl radical, C1-60Alkoxy, C containing substituents1-60Alkoxy, aryl containing substituent, alkyl aryl containing substituent, alkyl heteroaryl containing substituent, alkyl heterocyclic radical and alkyl heterocyclic radical containing substituent.
2. The organic semiconductor material according to claim 1,
said C containing a substituent2-60Substituents in the alkyl group are selected from: at least one of a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group;
said C containing a substituent1-60The substituent of the alkoxy, the aryl containing the substituent, the alkyl heteroaryl containing the substituent and the alkyl heterocyclic radical containing the substituent is selected from the following groups: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, hydroxy, mercapto, fluorogenAt least one of a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group.
3. The organic semiconductor material according to claim 1, wherein the alkoxy group is selected from the group consisting of: any one of methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy and eicosyloxy.
4. The organic semiconductor material of claim 1, wherein the aromatic group is selected from the group consisting of: at least one of phenyl, naphthyl, anthryl, phenanthryl, naphthacenyl, pentacenyl, trianilino, pyrenyl, indenyl, biphenyl, and fluorenyl.
5. The organic semiconductor material of claim 1, wherein the heterocyclic group and the heteroaromatic group are selected from the group consisting of: thiophene, benzothiophene, pyran, benzopyran, furan, benzofuran, imidazole, benzimidazole, pyrazole, benzopyrazole, pyrrole, benzopyrrole, pyridine, benzopyridine, pyrazine, benzopyrazine, indole, isoindole, benzindole, pyrimidine, benzopyrimidine, naphthyridine, benzonaphthyridine, pyridazine, benzopyridazine, indazole, benzindazole, purine, benzopyrurine, quinolizine, any of benzoquinolizine, quinoline, benzoquinoline, indolizine, benzaindolizine, phthalazine, benzophthalazine, quinoxaline, benzoquinoxaline, thiazole, benzothiazole, carboline, benzocarbazine, phenanthridine, benzophenanthridine, phenanthroline, benzophenanthroline, acridine, benzacridine, phenazine, benzophenazine, phenothiazine, carbazole, benzocarbazole, dithienopyrrole, tertiothiophene, tetrathiothiophene, and pentathiothiophene.
6. The organic semiconductor material of claim 1, wherein R is selected from C2-60Alkyl, C containing substituents2-60An alkyl group;
the substituents are selected from: at least one of a hydroxyl group, a mercapto group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a cyano group, an aldehyde group, an aliphatic group, a sulfo group, a sulfino group, a nitro group, an amino group, an imino group, a carboxyl group and a hydrazino group.
7. The organic semiconductor material of claim 6, wherein R is
Figure FDA0001725400890000021
The R is2、R3Is selected from C3-12Alkyl radical, R2、R3The same or different.
8. A method for synthesizing an organic semiconductor material according to any one of claims 1 to 7, comprising: the compound of the formula 2 is subjected to a yamamoto coupling reaction to obtain a compound of a formula 1;
Figure FDA0001725400890000023
9. the method of synthesizing as claimed in claim 8, wherein the condition of the yamamoto coupling reaction includes:
bis- (1, 5-cyclooctadiene) nickel as a catalyst; 1, 5-cyclooctadiene as a reducing agent; bipyridine as a ligand; tetrahydrofuran as a solvent;
preferably, the compound of formula 2 is prepared by the following steps:
carrying out bromination reaction on naphthalene hexacyclic to obtain a compound shown in a formula 3;
carrying out boron esterification reaction on the compound shown in the formula 3 and a boronizing reagent to obtain a compound shown in a formula 4;
reacting the compound shown in the formula 4 with 4-bromo-1, 8-naphthalic anhydride to obtain a compound shown in a formula 5;
carrying out a ring closure reaction on the compound of the formula 5 under the action of Lewis acid to obtain a compound of a formula 6;
compounds of formula 6 with R-NH2Reacting to form the corresponding compound of formula 7;
brominating the compound of formula 7 to obtain a compound of formula 2;
Figure FDA0001725400890000031
10. use of the organic semiconducting material of any of claims 1 to 7 in an organic opto-electronic device.
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