CN114920752A - Aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material and preparation method and application thereof - Google Patents

Aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material and preparation method and application thereof Download PDF

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CN114920752A
CN114920752A CN202210402810.4A CN202210402810A CN114920752A CN 114920752 A CN114920752 A CN 114920752A CN 202210402810 A CN202210402810 A CN 202210402810A CN 114920752 A CN114920752 A CN 114920752A
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unsubstituted
substituted
polycyclic aromatic
aromatic hydrocarbon
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赵保敏
黄维
李海洋
傅妮娜
汪联辉
储兴胜
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Nanjing University of Posts and Telecommunications
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
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    • 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
    • C07D471/22—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 systems contains four or more hetero rings
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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Abstract

The invention provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material, a preparation method and application thereof, wherein the semiconductor material has a structural general formula
Figure DDA0003600707570000011
The aza-highly distorted polycyclic aromatic hydrocarbon molecule core skeleton structure of the material is mainly synthesized by coupling an arylpyrrole unit and a symmetric tetrahalogen substituted core unit, subsequent Scholl oxidative dehydrogenation reaction and the like. The method realizes the high distortion of polycyclic aromatic hydrocarbon molecules by fusing aryl indole with electron donating property to form polycyclic aromatic hydrocarbon and introducing an intramolecular rigid steric hindrance method, and can effectively regulate and controlThe stacking behavior of the aza-condensed distorted polycyclic aromatic hydrocarbon in solution and solid film. The synthesis method is simple and easy, the synthesis yield is high, the structure is controllable, and the separation is easy; and the material can obtain brand new and wide application prospect in the fields of organic semiconductor devices, biosensing and the like.

Description

Aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic photoelectric semiconductors, and particularly relates to a nitrogen-condensed distorted polycyclic aromatic hydrocarbon semiconductor material and a preparation method and application thereof.
Background
Organic semiconductor materials have the advantages of being structurally related, solution processable, and processable on flexible substrates, and have become the host of a new generation of electronic information materials. The method has been widely focused and applied in the fields of organic light emitting diodes, organic field effect transistors, organic solar cells, perovskite solar cells, photoelectric detectors, biological sensing, diagnosis and treatment and the like. Research and development of a novel efficient organic conjugated semiconductor material inevitably leads to wide market prospect in the electronic industry.
Polycyclic aromatic hydrocarbons (Acenes) materials have unique structural features, can be considered as a local area of single-layer graphene, and have regular molecular structures and precise/single molecular weights. In addition, the one-dimensional or two-dimensional fused ring (1D/2 DFusedaceneohydroteracene) material shows extremely high device mobility. For example, Pentacene (Pentacene), Rubrene (Rubrene), Tetracene (Tetracene) derivatives and perylene imide (PDI) materials all have extremely high mobility, and the mobility is generally over 5cm 2 V.s. Therefore, these materials or their derivatives are being continuously expanded and applied in various fields. However, the polycyclic aromatic hydrocarbon with an all-benzene structure is mainly characterized by a linear structure, generally has the defects of poor stability, difficult functionalization, poor solubility and the like, and is not beneficial to solution processing and obtaining of a multi-scale regulated condensed state.
In addition, the polycyclic aromatic hydrocarbon with the conjugated skeleton all-carbon structure is doped with hetero atoms, so that a very interesting molecular structure and properties can be obtained. For example, in the field of organic light emitting diodes, the total carbon skeleton is doped with nitrogen atoms and boron atoms in a designed manner, so that a multi-resonance thermally activated delayed fluorescence material (MR-TADF) can be obtained. In addition, under specific conditions, the doping of nitrogen atoms can not only regulate and control the front-line orbital energy level of the polycyclic aromatic hydrocarbon, but also deeply influence the thermal, optical or electrical stability of corresponding molecules. Klaus mullen et al developed a variety of planar polycyclic aromatic hydrocarbons based on a carbon skeleton, which have strong intermolecular forces and, without the introduction of peripheral substituents, tend to exhibit very strong H-aggregation properties. No matter which linear polycyclic aromatic hydrocarbon is realized by adopting a high-temperature or transition metal catalysis mode, the synthesis steps are longer, the operation is complicated, the yield is lower, and the linear polycyclic aromatic hydrocarbon is not easy to be simply synthesized from commercial basic raw materials with controllability and high position selectivity.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material and a preparation method and application thereof, wherein commercial aryl pyrrole derivatives, aryl difluoro, aryl tetrafluoro, aryl dibromo, aryl tetrabromo and other derivatives are used as raw materials, the aza-distorted polycyclic aromatic hydrocarbon semiconductor material can be synthesized through reaction, other substituent group structures such as proper flexible alkyl chains are correspondingly introduced, the energy level and aggregation behavior of molecules can be adjusted, and the stability, solubility and solution processing property of the material are improved.
The purpose of the invention is realized by the following technical scheme:
an aza-fused distorted polycyclic aromatic hydrocarbon semiconducting material having a compound of the following general formula (I):
Figure BDA0003600707550000021
wherein, in the general formula (I), Ar is unsubstituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl;
Ar 1 、Ar 2 、Ar 3 、Ar 4 substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heteroaryl of C4-C30;
m and n are respectively and independently selected from integers of 0-6;
R 1 、R 2 、R 3 、R 4 each independently selected from hydrogen, deuterium, fluorine, chlorine, cyano, alkyl chain with C1-C24 straight chain or branched chain, thiophene or C1-C24 alkyl thiophene, phenyl
Figure BDA0003600707550000022
2, 6-dimethylphenyl
Figure BDA0003600707550000023
3, 5-dimethylphenyl
Figure BDA0003600707550000024
2, 6-diisopropylphenyl
Figure BDA0003600707550000025
4-tert-butylphenyl group
Figure BDA0003600707550000026
One of (1);
R 11 ，R 21 ，R 31 and R 41 Each independently selected from hydrogen, deuterium, fluorine, chlorine, cyano, alkyl chain with C1-C24 straight chain or branched chain, substituted or unsubstituted aryl with C6-C30, and substituted or unsubstituted heteroaryl with C4-C30;
、
Figure BDA0003600707550000031
wherein L is 1 Selected from single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar) 1 ，Ar 2 Each independently selected from substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, Ar 1 ，Ar 2 Are not linked to each other, or Ar 1 And Ar 2 The N to which it is attached forms a nitrogen-containing heterocycle.
Preferably, Ar is unsubstituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzopyrimidinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothiophenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted naphtholyl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthoindolyl, substituted or unsubstituted thienoindolyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dithienophenyl, substituted or unsubstituted dithienyldinaphthenyl, Substituted or unsubstituted dithiophene perylene group and substituted or unsubstituted naphthalimide group.
Preferably, Ar is 1 、Ar 2 、Ar 3 、Ar 4 Unsubstituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted thienyl, substituted or unsubstituted bithiopheneyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthylfluoryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthoindolyl, substituted or unsubstituted thienoindolyl, substituted or unsubstituted pyrenyl;
ar is one of the following aromatic structures:
Figure BDA0003600707550000041
pyrene
Figure BDA0003600707550000042
2, 7-di-tert-butylpyrene
Figure BDA0003600707550000043
(1, 8-ba: 4,5-a 'b') naphthothiophene
Figure BDA0003600707550000044
Naphthalene tetracarboxylic acid diimide
Figure BDA0003600707550000045
Benzoimides
Figure BDA0003600707550000046
And the following structure:
Figure BDA0003600707550000047
preferably, Ar is 1 ，Ar 2 Each independently is phenyl, thienyl, biphenyl, fluorenyl, carbazolyl, benzofuranyl, benzothienyl, pyridyl, pyrimidinyl, phenanthryl, anthracyl, and phenyl, thienyl, biphenyl, fluorenyl, carbazolyl, benzofuranyl, benzothienyl, pyridyl, pyrimidinyl, phenanthryl, anthracyl substituted with deuterium, fluoro, cyano, methyl, t-butyl, hexyl, octyl, isooctyl; l is 1 Is one of single bond, phenyl, tolyl, xylyl, thienyl, pyrimidinyl, pyridyl, fluorenyl, carbazolyl, furyl, phenanthryl, benzothienyl, benzofuryl and dibenzofuryl.
Preferably, the compound of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is any one of the following compounds, but not limited to the following structures:
Figure BDA0003600707550000051
Figure BDA0003600707550000061
preferably, the synthesis reaction formula of the preparation method of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is shown as follows,
Figure BDA0003600707550000062
the synthesis method comprises the following core steps:
step one, C-N coupling between pairwise paired aryl halohydrocarbon derivatives S1 and substituted or unsubstituted aryl pyrrole derivatives S2 to obtain a key intermediate S3;
and step two, carrying out dehydrocoupling reaction on the key intermediate S3 on a pyrrole ring to obtain the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material S4. Of course, the compound can also be an intermediate containing functional groups such as halogen, carboxyl and the like, and the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material represented by the general formula (I) can be obtained through simple other coupling reactions.
Preferably, in the first step, if fluorine atoms exist in the S1 structural unit, the reaction conditions of the first step are as follows: reacting 1 equivalent of S1, 4-5 times of S2 and 4.5-5.5 times of NaH in tetrahydrofuran, N-dimethylformamide or dioxane at room temperature or at the lower temperature of-15-0 ℃;
if the structure of S1 is bromine, iodine or chlorine atom, the condition of the first step is as follows: 1 equivalent of S1, 4-5 times equivalent of S2, 7.5-9 times equivalent of potassium tert-butoxide (or sodium tert-butoxide), 0.3-2% equivalent of palladium catalyst and 1.2-8% equivalent of phosphine ligand, and reacting in anhydrous toluene, anhydrous dioxane or anhydrous DMF at 85-135 ℃ for 2-24 hours;
the step of reacting the di, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, trifluoromethanesulfonic acid or trifluoroacetic acid and dichloromethane at 0-60 ℃ for 2-18 hours or reacting the 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and ScTf 2 Dichloromethane, 0 ℃ to 60 ℃ for 2 hours to 18 hours, or other Scholl reaction conditions.
Preferably, the reaction process of the step one and the step two is protected by inert gas, and the inert gas is nitrogen or argon.
Preferably, the application of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is characterized in that: the method is applied to organic photoelectric devices.
Preferably, the active optoelectronic devices comprise organic light emitting diode devices, organic thin film transistor devices, organic solar cell devices, perovskite solar cell devices; the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is applied as a charge transport layer in a functional layer of an organic light-emitting diode; the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is used as an active layer in an active layer of an organic thin film transistor; the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is used as a hole transport layer in a perovskite solar cell composition; the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is used as an active layer additive in an organic solar cell composition.
According to the invention, nitrogen atoms are introduced into the polycyclic aromatic hydrocarbon system with an all-benzene structure for doping, so that the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is obtained, and the nitrogen-condensed distorted polycyclic aromatic hydrocarbon semiconductor material has high innovativeness and value. The aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material has unique molecular structure, aggregation behavior and physicochemical properties. By introducing intramolecular tension and steric hindrance into the plane rigid structures, plane distortion of molecules can be effectively regulated, and the regulation of a condensed state of the molecules is obtained, so that more excellent physical properties such as photoelectromagnetism and the like are obtained.
By fusing the aryl pyrrole derivative to form polycyclic aromatic hydrocarbon and introducing an intramolecular rigid steric hindrance method, high distortion of polycyclic aromatic hydrocarbon molecules is realized, and the problems of fluorescence efficiency reduction and the like caused by common aggregation of perylene imide derivatives in a solution or a solid film can be effectively inhibited. The synthesis method is simple and easy to implement, high in synthesis yield, controllable in structure and easy to separate.
The aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material provided by the invention has adjustable spectral band gap and can be processed by solution, can be used as a conjugated organic semiconductor to be applied to the photoelectric semiconductor field and the biomedical field, and has brand new and wide application prospect.
Drawings
FIG. 1: the high-resolution mass spectrum of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4NP-TPN precursor c2 in the embodiment 2 of the invention.
FIG. 2 is a schematic diagram: the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4NP-TPN high resolution mass spectrogram in the embodiment 2 of the invention.
FIG. 3: ultraviolet absorption spectrum and fluorescence emission spectrum of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4NP-TPN precursor c2 in example 2 of the invention.
FIG. 4: the fluorescence emission spectrum of the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4NP-TPN in the embodiment 2 of the invention.
Detailed Description
The invention discloses an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material, a preparation method and application thereof, which are described in combination with specific examples for better understanding of the invention.
In the present specification, when a definition is not otherwise provided, "substituted" means that at least one hydrogen of a substituent or a compound is replaced with deuterium, halogen, cyano, substituted or unsubstituted C1 to C24 alkyl, C3 to C30 cycloalkyl, C6 to C30 aryl, C2 to C30 heteroaryl, or a combination thereof. Specifically, in particular examples of the present invention, "substituted" means that at least one hydrogen of the substituent or compound is replaced with D, F, Cl, CN, CH 3 -, tert-butyl, pyridyl, phenyl, naphthyl, phenanthryl, anthracyl, fluorenyl, carbazolyl, triphenylamino, pyrimidinyl, triazinyl, benzopyrazinyl, benzofuranyl, dibenzofuranyl, dibenzothienyl, indolyl, indolocarbazolyl.
In the present specification, when a definition is not otherwise provided, "hetero" means including 1 to 2 hetero atoms selected from N, O, S, P and Si and the remaining carbon in one functional group.
In the present specification, when a definition is not otherwise provided, "alkyl" refers to an aliphatic hydrocarbon group. The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain and may be selected from methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert-butyl.
Specific examples of the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
In this specification, "aryl" refers to a group that includes at least one hydrocarbon aromatic moiety, and all elements of the hydrocarbon aromatic moiety have p-orbitals that form conjugates, such as phenyl, naphthyl, and the like, two or more hydrocarbon aromatic moieties may be joined by sigma bonds and may be, for example, biphenyl, terphenyl, quaterphenyl, and the like, or two or more hydrocarbon aromatic moieties may be fused, directly or indirectly, to provide a non-aromatic fused ring. For example, it may be fluorenyl. Aryl groups can include monocyclic, polycyclic, or fused-ring polycyclic (i.e., rings that share adjacent pairs of carbon atoms) functional groups.
In the present specification, "heterocyclic group" is a general concept of heteroaryl group, and at least one heteroatom selected from N, O, S, P and Si may be included in a cyclic compound such as aryl group, cycloalkyl group, a fused ring thereof, or a combination thereof, instead of carbon (C). When the heterocyclyl group is a fused ring, the entire ring or each ring of the heterocyclyl group may contain one or more heteroatoms. For example, "heteroaryl" refers to an aryl group that includes at least one heteroatom selected from N, O, S, P and Si. Two or more heteroaryl groups are directly linked by a sigma bond, or when a heteroaryl group comprises two or more rings, the two or more rings may be fused. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms. Specific examples of the heterocyclic group may be, but are not limited to, a pyridyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolyl group, an isoquinolyl group, a substituted or unsubstituted phenoxazinyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.
Example 1
This example provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4MBP-PyCN and its preparation method, the synthetic route is shown below,
Figure BDA0003600707550000091
synthesis of intermediate c 1: in a two-necked round bottom flask (150mL) were added b1(6.60g, 50mmol) and 70mL anhydrous Tetrahydrofuran (THF) and NaH (2.2g, 60%Dispersed in mineral oil) was added in four portions and stirred at room temperature for 40 minutes. A further two-necked round-bottomed flask (150mL) was taken and a1(1.93g, 11mmol) was dissolved in 20mL anhydrous THF. And (3) dropwise adding the reaction solution of b1 and NaH into the solution of a1 under the protection of nitrogen, reacting for 8 hours at room temperature, and adding 5mL of ethanol to quench the reaction. Most THF is removed by rotary evaporation, the obtained reaction liquid is extracted by dichloromethane, an organic phase is washed for three times by saturated solution of sodium chloride, after drying by anhydrous sodium sulfate, the pressure reduction and concentration are carried out, the obtained solid is separated by a column chromatography method, and the volume ratio of eluent is dichloromethane: petroleum ether is 1: 2, 5.5g of the yellow-green product compound c1 was obtained in 81% yield. HR-MS (ACPI-M) + ,m/z)：621.2691。
Synthesis of 4 MBP-PyCN: in a two-necked round-bottomed flask (150mL), the product compound c1 from the above step (1.25g, 2mmol) was dissolved in anhydrous dichloromethane, DDQ (2.8g,12.5mmol) was added thereto, 4.5mL of trifluoromethanesulfonic acid was added dropwise thereto under stirring in an ice-water bath at 0 ℃ and after stirring for 30 minutes, stirring was continued at room temperature for 6 hours. Adding hydrazine hydrate to digest residual DDQ, extracting with chloroform, washing organic phase with saturated solution of sodium chloride for three times, drying with anhydrous sodium sulfate, concentrating under reduced pressure, separating the obtained solid with column chromatography to obtain product, wherein the volume ratio of eluent is dichloromethane: petroleum ether is 1: 2, after column chromatography, slurried with ethyl acetate to give 0.98g of a pure bright yellow-green solid in 78% yield. HR-MS (ACPI-M) + ,m/z)：617.2386。
Example 2
The embodiment provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4NP-TPN and a preparation method thereof, wherein the synthetic route is as follows:
Figure BDA0003600707550000101
synthesis of intermediate c 2: in a two-necked round-bottomed flask (150mL), b2(9.18g, 55mmol) and 60mL anhydrous Tetrahydrofuran (THF) were added and NaH (2.4g, 60% in mineral oil) was added in four portions and stirred at room temperature for 40 minutes. A further two-necked round-bottomed flask (150mL) was taken and a2(2.40g, 12mmol) was dissolved in 30mL anhydrous THF. Will be provided withAnd b2 and NaH are added into the solution of a2 dropwise under the protection of nitrogen, the mixture is reacted for 12 hours at room temperature, and 5mL of ethanol is added to quench the reaction. Removing most THF by rotary evaporation, adding a large amount of water to obtain a dark green solid, pulping by using ethanol to obtain yellow green powder, separating the product of the obtained solid powder by using a column chromatography method, wherein the volume ratio of the eluent is dichloromethane: petroleum ether is 1: 2, 7.84g of a yellow-green product, compound c2, are obtained, yield 83%. HR-MS (ACPI-M) + ,m/z)：789.2823。
Synthesis of 4 NP-TPN: in a two-necked round-bottomed flask (150mL), the product compound c1 from the above step (1.60g,2mmol) was dissolved in anhydrous dichloromethane, DDQ (2.8g,12.5mmol) was added thereto, 4.5mL of trifluoromethanesulfonic acid was added dropwise thereto under stirring in an ice-water bath at 0 ℃ and after stirring for 30 minutes, stirring was continued at room temperature for 6 hours. Adding hydrazine hydrate to digest residual DDQ, adding a large amount of methanol, settling the product, filtering out solids, washing filter cakes with water and methanol respectively, and separating the product from the obtained solids by a column chromatography method, wherein the volume ratio of the eluent is dichloromethane: petroleum ether is 1: 2, after column chromatography, slurried with ethyl acetate to give pure 1.44g of a bright yellow solid in 90% yield. HR-MS (ACPI-M) + ,m/z)：785.2382。
Example 3
This example provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 4PPyr-NI and a preparation method thereof, and the synthetic route thereof is as follows:
Figure BDA0003600707550000102
synthesis of intermediate c 3: b3(10.62g, 55mmol), a3(10.8g,12mmol), sodium tert-butoxide (13.0g, 135mmol), Pd2dba3(184mg, 0.2mmol), Sphos (187mg,0.4mmol) and 200mL of anhydrous toluene were added to a two-necked round bottom reaction flask (500mL), heated and stirred at 120 ℃ for 8 hours under nitrogen, cooled, flash column filtered to remove inorganic salts and residual palladium catalyst, slurried with acetone and ethyl acetate, and recrystallized with a toluene-cyclohexane mixture to give c3 as a red solid, 12.32g, 76% yield. HR-MS (ACPI-M) + ,m/z)：1350.5780。
4, synthesis of PPyr-N: in a two-necked round-bottomed flask (150mL), the product compound c3 from the above step (2.70g,2mmol) was dissolved in anhydrous dichloromethane, DDQ (2.8g,12.5mmol) was added thereto, 4.5mL of trifluoromethanesulfonic acid was added dropwise thereto under stirring in an ice-water bath at 0 ℃ and after stirring for 30 minutes, the temperature was raised to 60 ℃ and stirring was continued for 8 hours. Cooling to room temperature, adding hydrazine hydrate to digest residual DDQ, adding a large amount of methanol, settling the product, filtering out solids, washing filter cakes with water and methanol respectively, and separating the product from the obtained solids by using a column chromatography method, wherein the volume ratio of the eluent is dichloromethane: petroleum ether 2: 3, after column chromatography, slurried with ethyl acetate to give 2.24g of a pure bright yellow solid in 83% yield. HR-MS (ACPI-M) + ，m/z)：1346.5465。
Example 4
The embodiment provides an aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material 2TPA-2MePyr-Cz and a preparation method thereof, the synthetic route of which is shown as follows,
Figure BDA0003600707550000111
synthesis of intermediate c 4: in a two-necked round-bottomed flask (250mL), b1(2.88g, 22mmol), a4(8.12g,10mmol), sodium tert-butoxide (6.0g, 62mmol), Pd were added 2 dba 3 (92mg,0.1mmol), Sphos (94mg, 0.2mmol) and 80mL of anhydrous toluene, heating and stirring at 80 ℃ for 8 hours under the protection of nitrogen, cooling the reaction solution, filtering with a flash column to remove inorganic salts and residual palladium catalyst to obtain an off-white solid, and carrying out column chromatography to obtain a white solid c4, 5.6g and the yield is 68%. HR-MS (ACPI-M) + ,m/z)：819.2770。
Synthesis of key intermediate c 5: in a two-necked round-bottomed flask (250mL), the product of the above step, compound c4(4.1g,5mmol), b4(4.5g,12.5mmol), sodium tert-butoxide (6.6g, 68mmol), Pd 2 dba 3 (150mg,0.15mmol), Sphos (150mg,0.3mmol) and 80mL of anhydrous toluene, heating and stirring at 120 ℃ for 8 hours under the protection of nitrogen, cooling the reaction solution, filtering by a flash column to remove inorganic salts and residual palladium catalyst, and concentrating to obtain brown oily viscous liquidLiquid and column chromatography gave c5 as a white solid, 5.65g, 82% yield. HR-MS (ACPI-M) + ,m/z)：1379.7497。
Synthesis of 2TPA-2 MePyr-Cz: c5(2.8g, 2mmol) was dissolved in dry dichloromethane, DDQ (2.8g,12.5mmol) was added thereto, 4.5mL trifluoromethanesulfonic acid was added dropwise thereto with stirring in a 0 ℃ ice water bath, and after stirring for 30 minutes, the temperature was raised to 40 ℃ and stirring was continued for 8 hours. Cooling to room temperature, adding hydrazine hydrate to digest residual DDQ, adding a large amount of methanol, settling the product, filtering out solids, washing filter cakes with water and methanol respectively, and separating the product from the obtained solids by using a column chromatography method, wherein the volume ratio of the eluent is dichloromethane: petroleum ether is 1: 3, after column chromatography, slurried with ethyl acetate to give pure 2.06g of a bright yellow solid in 73.5% yield. HR-MS (ACPI-M) + ,m/z)：1375.7185。
Characterization test
For all the embodiments, firstly, the last step of reaction is realized through an oxidative dehydrogenation ring closing step, and the successful implementation of the step is on the premise that the precursor structures of the final products of all the embodiments are correct; secondly, target molecules obtained by the ring closure reaction in all the examples have very similar mother-nucleus rigid frameworks, and the difference of the structures of the target molecules can cause the difference of the optical spectrum, the electrochemical energy level and the like, but, as known by a person skilled in the art, the test of ultraviolet visible spectrum absorption and fluorescence spectrum emission in a solvent and the high-molecular resolution mass spectrometry test and the like on the target molecules are all general methods for the structural characterization of organic semiconductor molecules, and are not only suitable for the rigid twisted semiconductor molecules described in the patent of the invention, but also suitable for the test of any other conjugated organic semiconductor molecules, therefore, the invention can select one example, the test result of which is representative, and is suitable for all the examples of the invention and other structures which are not shown by the examples.
Example 2 was selected for representative characterization tests below, and the macromolecule resolution spectrum of key intermediate c2 of example 2 is shown in fig. 1; the high resolution mass spectrum of the aza-condensed polycyclic aromatic hydrocarbon 4NP-TPN provided in example 2 is shown in FIG. 2; comparing fig. 1 and fig. 2, it can be seen that the synthesis conditions of 4NP-TPN provided in example 2 can obtain the desired aza-condensed polycyclic aromatic hydrocarbon with high efficiency.
The uv absorption spectrum and the fluorescence spectrum of the key intermediate c2 of example 2 are shown in fig. 3, in which fig. 3, the abscissa indicates the wavelength, the left ordinate indicates the normalized absorption intensity, the right ordinate is the normalized emission spectrum, and the maximum emission wavelength of the emission spectrum of c2 is 557 nm.
The fluorescence emission spectrum of aza-condensed polycyclic aromatic hydrocarbon 4NP-TPN provided in example 2 is shown in FIG. 4, wherein the abscissa of FIG. 4 represents wavelength and the ordinate represents intensity. The maximum emission peak wavelength of fluorescence emission of 4NP-TPN is 539 nm. As can be seen from a comparison of FIGS. 3 and 4, the fluorescence emission spectrum of 4NP-TPN after fusion to form polycyclic aromatic hydrocarbons is more blue-shifted than that of its precursor c2 due to the increase in the rigidity of the molecule after fusion.
The invention obtains the aza-condensed polycyclic aromatic hydrocarbon semiconductor material by introducing a pyrrole aromatic hydrocarbon structure into polyhalogenated aromatic hydrocarbon and carrying out hydrogen oxidation and dehydrogenation on the pyrrole activity of a corresponding intermediate, wherein the aza-condensed polycyclic aromatic hydrocarbon semiconductor molecule has high-density packing and ring tension in molecules, thereby causing molecular distortion, and the high aza-condensed polycyclic aromatic hydrocarbon semiconductor molecule has new and unique optical and electrical characteristics and has very important significance.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (9)

1. An aza-fused distorted polycyclic aromatic hydrocarbon semiconductor material, characterized by: the structure of the compound is as the following general formula (I):
Figure FDA0003600707540000011
wherein, in the general formula (I), Ar is unsubstituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl;
Ar 1 、Ar 2 、Ar 3 、Ar 4 unsubstituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C4-C30 heteroaryl;
m and n are respectively and independently integers from 0 to 6;
R 1 、R 2 、R 3 、R 4 each independently selected from one of hydrogen, deuterium, fluorine, chlorine, cyano, alkyl chain with C1-C24 straight chain or branched chain, thiophene or C1-C24 alkyl thiophene, phenyl, 2, 6-dimethylphenyl, 3, 5-dimethylphenyl, 2, 6-diisopropylphenyl and 4-tert-butylphenyl;
R 11 ，R 21 ，R 31 and R 41 Each independently selected from hydrogen, deuterium, fluorine, chlorine, cyano, alkyl chain with C1-C24 straight chain or branched chain, substituted or unsubstituted aryl with C6-C30, substituted or unsubstituted heteroaryl with C4-C30,
Figure FDA0003600707540000012
Wherein L is 1 Selected from single bond, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; ar (Ar) 1 ，Ar 2 Each independently selected from substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, Ar 1 ，Ar 2 Are not linked to each other, or Ar 1 And Ar 2 The N to which it is attached forms a nitrogen-containing heterocycle.
2. An aza-fused contorted polycyclic aromatic hydrocarbon semiconducting material as claimed in claim 1, wherein: ar is substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted benzopyrimidinyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted thienyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthylfluoro, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthoindolyl, substituted or unsubstituted thienoindolyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted triphenylenyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted dithienophenyl, substituted or unsubstituted dithienylrylnaphthyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolyl, or substituted or unsubstituted quinolyl, or substituted or unsubstituted quinolyl, or substituted or unsubstituted benzothienyl, or substituted, Substituted or unsubstituted dithiophene perylene group and substituted or unsubstituted naphthalimide group.
3. An aza-fused contorted polycyclic aromatic hydrocarbon semiconducting material as claimed in claim 1, wherein: ar is 1 、Ar 2 、Ar 3 、Ar 4 Unsubstituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted quinazolinyl, substituted or unsubstituted thienyl, substituted or unsubstituted bithiopheneyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthryl, substituted or unsubstituted phenanthryl, substituted or unsubstituted naphthylfluoryl, substituted or unsubstituted fluorenyl, substituted or unsubstituted naphthoindolyl, substituted or unsubstituted thienoindolyl, substituted or unsubstituted pyrenyl;
ar is one of the following aromatic structures:
Figure FDA0003600707540000021
Figure FDA0003600707540000031
4. as claimed in claim 1The aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material is characterized in that: ar is 1 ，Ar 2 Each independently phenyl, thienyl, biphenyl, fluorenyl, carbazolyl, benzofuranyl, benzothienyl, pyridyl, pyrimidinyl, phenanthryl, anthracyl, and phenyl, thienyl, biphenyl, fluorenyl, carbazolyl, benzofuranyl, benzothienyl, pyridyl, pyrimidinyl, phenanthryl, anthracyl substituted with deuterium, fluoro, cyano, methyl, t-butyl, hexyl, octyl, isooctyl; l is 1 Is one of single bond, phenyl, tolyl, xylyl, thienyl, pyrimidinyl, pyridyl, fluorenyl, carbazolyl, furyl, phenanthryl, benzothienyl, benzofuryl and dibenzofuryl.
5. An azacondensed distorted polycyclic aromatic hydrocarbon semiconductor material as claimed in any one of claims 1 to 4, wherein: the compound is any one of the following compounds, but is not limited to the following structure:
Figure FDA0003600707540000032
Figure FDA0003600707540000041
6. a method of preparing an aza-fused distorted polycyclic aromatic hydrocarbon semiconducting material as claimed in any of claims 1 to 4, wherein: the synthesis reaction formula is shown as follows,
Figure FDA0003600707540000051
the synthesis method comprises the following core steps:
step one, C-N coupling between pairwise paired aryl halohydrocarbon derivatives S1 and substituted or unsubstituted arylpyrrole derivatives S2 to obtain a key intermediate S3;
and step two, carrying out dehydrocoupling reaction on the key intermediate S3 on a pyrrole ring to obtain the aza-condensed distorted polycyclic aromatic hydrocarbon semiconductor material S4.
7. The method of claim 6, wherein the azafused distorted polycyclic aromatic hydrocarbon semiconductor material is prepared by: in the first step, if fluorine atoms exist in the S1 structural unit, the reaction conditions of the first step are as follows: reacting 1 equivalent of S1, 4-5 times equivalent of S2 and 4.5-5.5 times equivalent of NaH in tetrahydrofuran, N-dimethylformamide or dioxane at room temperature or at a low temperature of-15-0 ℃;
if the structure of S1 is bromine, iodine or chlorine atom, the condition of the first step is as follows: 1 equivalent of S1, 4-5 times equivalent of S2, 7.5-9 times equivalent of potassium tert-butoxide (or sodium tert-butoxide), 0.3-2% equivalent of palladium catalyst and 1.2-8% equivalent of phosphine ligand, and reacting in anhydrous toluene, anhydrous dioxane or anhydrous DMF at 85-135 ℃ for 2-24 hours;
the step of reacting the di, 2, 3-dichloro-5, 6-dicyan-p-benzoquinone, trifluoromethanesulfonic acid or trifluoroacetic acid and dichloromethane at 0-60 ℃ for 2-18 hours or reacting the 2, 3-dichloro-5, 6-dicyan-p-benzoquinone and ScTf 2 And reacting at 0-60 ℃ for 2-18 hours by using dichloromethane.
8. A method of preparing an aza-fused contorted polycyclic aromatic semiconductor material as claimed in claim 7, wherein: and in the reaction processes of the first step and the second step, inert gas is used for protection, and the inert gas is nitrogen or argon.
9. Use of an aza-fused contorted polycyclic aromatic hydrocarbon semiconducting material as claimed in any of claims 1 to 4, wherein: the method is applied to organic photoelectric devices.
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