Functionalized indanone condensed aza-acene organic semiconductor material as well as preparation method and application thereof

Abstract

The invention discloses a functional indanone condensed aza-acene organic semiconductor material as well as a preparation method and application thereof, and belongs to the technical field of organic semiconductor materials. The organic semiconductor material is prepared by functionalizing indanone by using a strong electron withdrawing group and then condensing with an aza-acene unit containing sp2 hybridized nitrogen atoms. The organic semiconductor material has low LUMO energy level and high stability, has the capability of stably transmitting electrons in air, and is suitable for being used as an active material and an electron transmission material in organic photoelectric devices.

Description

Technical Field

[0001] The present invention belongs to the field of organic semiconductor materials, and particularly relates to a functionalized indanone-fused azapentacene organic semiconductor material, a preparation method thereof, and an application thereof. Background Art

[0002] Polyacene materials are composed of multiple benzene rings linearly fused to form a class of polycyclic aromatic hydrocarbon compounds with unique structures. Due to their large π-conjugated systems and strong π-π interactions, these compounds exhibit high molecular structure regularity and excellent planarity, and thus show excellent optoelectronic properties. In recent years, remarkable progress has been made in the research and development of the synthesis and application technologies of high-performance polyacene materials. Common linear polyacene organic compounds, such as tetracene and pentacene, have been widely used in the active layers of organic optoelectronic devices, including organic field effect transistors, organic light-emitting diodes, organic photodetectors, and organic solar cells.

[0003] Traditional polyacene materials mainly exhibit p-type charge transport properties. In contrast, n-type polyacene materials are relatively scarce. In organic optoelectronic devices, both p-type and n-type semiconductor materials play indispensable roles. Therefore, it is particularly important to design and prepare new n-type polyacene materials. Introducing different numbers and positions of sp 2 hybrid nitrogen atoms into the acene structure can effectively lower the LUMO energy level of the molecule and adjust its charge transport performance. Therefore, azapentacene has important potential in the development of n-type organic semiconductor materials. On the other hand, when the number of nitrogen atoms and aromatic rings in the azapentacene structure is too large, its stability will decrease. Therefore, it is of great significance to develop new molecular synthesis strategies to construct new azapentacene organic semiconductor materials, which have important application prospects in organic optoelectronic devices. Summary of the Invention

[0004] The purpose of the present invention is to provide a functionalized indanone-fused azapentacene organic semiconductor material, a preparation method thereof, and an application thereof. By functionalizing indanone with an electron-withdrawing group, the present invention can further lower the overall LUMO energy level of the molecule. The organic semiconductor material constructed by fusing the functionalized indanone with an azapentacene unit will have the optoelectronic properties of azapolyacene materials and can be used as an active material and an electron transport material in organic optoelectronic devices.

[0005] The functionalized indanone-fused azapentacene of the present invention has the following general formula I:

[0006]

[0007] In the general formula:

[0008] Ar represents any one of the following groups:

[0009]

[0010] The dotted line indicates the connection position of the group.

[0011] R1 is selected from a hydrogen atom, a cyano group, a halogen group, an alkyl group, a silyl group, an alkoxy group or an aryl group.

[0012] Furthermore, the halogen group is an iodine atom, a bromine atom, a chlorine atom or a fluorine atom; the alkyl group is a C1-C 40 linear alkyl group or a C3-C 40 branched alkyl group; the silyl group is (CH3)3SiC≡C*, (CH2CH3)3SiC≡C*, ((CH3)2CH)3SiC≡C*, where * represents the connection direction; the alkoxy group is -OR2, and in the alkoxy group, R2 is a C1-C 40 linear alkyl group or a C3-C 40 branched alkyl group; the aryl group is benzene, naphthalene, anthracene, pyridine, pyrazine, quinoxaline or phenazine and their derivatives.

[0013] The preparation method of the functionalized indanone-fused azabenzene of the present invention comprises the following steps:

[0014] Step 1: Preparation of the amino compound

[0015] 1a-1: Dissolve the amino-protected compound shown in Formula II and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir for reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 1: 2R1(C6H2)N2S or 2R1(C 10 H4)N2S or 2R1(C4N2)N2S or 2R1(C8H2N2)N2S. The structure of the R1-functionalized compound 1 is shown as follows:

[0016] .

[0017] The definition of Ar is the same as above.

[0018] 1a-2: Dissolve the R1-functionalized compound 1 obtained in 1a-1 in a second organic solvent, add lithium aluminum hydride as a reducing agent, stir at room temperature for a reduction reaction. After the reaction is completed, quench the reaction with a saturated NH4Cl solution, extract the organic phase with dichloromethane, separate the liquid, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the amino compound 1: 2R1(C6H2)N2H4 or 2R1(C 10(H4)N2H4 or 2R1(C4N2)N2H4 or 2R1(C8H2N2)N2H4. The structure of the amino compound 1 is shown as follows:

[0019] .

[0020] 1b-1: Dissolve the amino-protected compound shown in Formula III and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir for reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 2: 2R1(C6H2)C 20 H 36 N2O8 or 2R1(C 10 H4)C 20 H 36 N2O8 or 2R1(C4N2)C 20 H 36 N2O8 or 2R1(C8H2N2)C 20 H 36 N2O8. The structure of the R1-functionalized compound 2 is shown as follows:

[0021] .

[0022] 1b-2: Dissolve the R1-functionalized compound 2 obtained in 1b-1 in a second organic solvent, add trifluoroacetic acid, stir at room temperature for deprotection reaction. After the reaction is completed, quench the reaction with saturated Na2CO3 solution, extract the organic phase with dichloromethane, separate the liquid, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the amino compound 2: 2R1(C6H2)N2H4 or 2R1(C 10 H4)N2H4 or 2R1(C4N2)N2H4 or 2R1(C8H2N2)N2H4. The structure of the amino compound 2 is shown as follows:

[0023] .

[0024] Step 2: Preparation of the functionalized indanone compound

[0025] Dissolve ninhydrin, malononitrile, and piperidine in a third organic solvent, heat and stir for condensation reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the functionalized indanone compound.

[0026] The structure of the functionalized indanone compound is shown as follows:

[0027]

[0028] Step 3: Preparation of functionalized indanone-fused azabenzene

[0029] Dissolve the amino compound 1 or amino compound 2 prepared in Step 1 and the functionalized indanone compound prepared in Step 2 in a fourth organic solvent, heat and stir for a condensation reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the functionalized indanone-fused azabenzene, which is the target product shown in Formula I.

[0030] The protected amino compound is selected from any one of the following compounds of Formula II or Formula III:

[0031]

[0032] Wherein:

[0033] Ar' is selected from any one of the following groups:

[0034]

[0035] R3 is a hydrogen atom, a cyano group or a halogen group. The dotted line indicates the connection position of the group.

[0036] The halogen group is an iodine atom, a bromine atom, a chlorine atom or a fluorine atom.

[0037] The R1 functionalized raw material is a C1-C 40 linear alkyl or a C3-C 40 branched alkyl corresponding halogenated compound, wherein the halogen group is an iodine atom, a bromine atom, a chlorine atom or a fluorine atom; or is trimethylsilylacetylene, triethylsilylacetylene or triisopropylsilylacetylene; or is a C1-C 40 linear alkyl or a C3-C 40 branched alkyl corresponding alcohol; or is benzene, naphthalene, anthracene, pyridine, pyrazine, quinoxaline or phenazine and their derivatives corresponding boric acid or borate ester, and their corresponding organotin reagents.

[0038] The present invention applies the functionalized indanone-fused azabenzene as an organic semiconductor material to an organic optoelectronic device.

[0039] The organic optoelectronic device includes an organic field effect transistor, an organic light emitting diode, an organic photodetector or an organic solar cell.

[0040] The present invention provides a functionalized indanone-fused azabenzene organic semiconductor material having the structure shown in Formula I. By fusing the functionalized indanone and azabenzene units, while increasing the conjugation degree of the material, good stability is obtained. The sp 2Hybrid nitrogen atoms can reduce the electron cloud density of the molecule and lower the LUMO energy level of the material. On the other hand, for the functionalized indanone-fused azabenzacene compound with the structure shown in Formula I, in addition to the electron-withdrawing sp 2 hybrid nitrogen atoms, there are other strong electron-withdrawing groups, which further lower the LUMO energy level of the molecule and enable air-stable electron transport in organic optoelectronic devices. At the same time, the functional groups possessed by this material can improve its solubility in organic solvents, which is beneficial for its solution processing. Therefore, the functionalized indanone-fused azabenzacene organic semiconductor material with the structure shown in Formula I provided by the present invention has broad application prospects and high application value in organic optoelectronic devices.

[0041] The present invention also provides a preparation method for the functionalized indanone-fused azabenzacene compound with the structure shown in Formula I. The method provided by the present invention is simple to operate and has a high product yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 It is a schematic diagram of an organic field-effect transistor structure; wherein: (a) bottom-gate top-contact type; (b) bottom-gate bottom-contact type; (c) top-gate top-contact type; (d) top-gate bottom-contact type.

[0043] Figure 2 It is the 1H NMR spectrum of Compound 36-DBNM prepared in Example 1.

[0044] Figure 3 It is the 13C NMR spectrum of Compound 36-DBNM prepared in Example 1.

[0045] Figure 4 It is the 1H NMR spectrum of Compound DPNM prepared in Example 2.

[0046] Figure 5 It is the 13C NMR spectrum of Compound DPNM prepared in Example 2.

[0047] Figure 6 It is the corresponding ultraviolet-visible absorption spectrum of Compound 36-DBNM prepared in Example 1 and Compound DPNM prepared in Example 2 in DCM; the starting points (λ onset ) of the absorption edges of 36-DBNM and DPNM are 538 nm and 588 nm respectively. According to the formula E g = 1240 / λ oneset , the optical band gaps (E g ) of 36-DBNM and DPNM can be calculated to be 2.30 eV and 2.11 eV.

[0048] Figure 7Figure 0 shows the cyclic voltammograms of compounds 36-DBNM and DPNM in DCM. Both compounds exhibit reversible reduction peaks, but no oxidation peaks are observed. The half-wave potential E 1 / 2 (versus FeCp2 + / FeCp2 (Fc + / Fc)) of the reduction peak of 36-DBNM is 1.01 V. According to the equation E LUMO = (-4.80 - E 1 / 2 ) eV (where -4.80 is the energy level of ferrocene in vacuum and E 1 / 2 is the half-wave potential relative to ferrocene), the LUMO energy level of 36-DBNM can be calculated to be -3.80 eV;

[0049] The onset potential E onest (versus FeCp2 + / FeCp2 (Fc + / Fc)) of the reduction peak of DPNM is 0.89 V. According to the equation E LUMO = (-4.80 - E onest ) eV (where -4.80 is the energy level of ferrocene relative to the vacuum energy level and E onest is the first potential relative to ferrocene), the LUMO energy level of DPNM can be calculated to be -3.91 eV.

[0050] Figure 8 Figure 31 shows the frontier molecular orbitals and energy levels of compounds 36-DBNM and DPNM in the gas phase calculated by DFT with the B3LYP / 6-311G** basis set. Gaussian 09 (with the B3LYP / 6-311G** basis set) was used to calculate the molecules, and the electron cloud distributions of the HOMO and LUMO of compound 36-DBNM were simulated. To optimize the calculation efficiency, the groups on the silicon atoms were replaced by methyl groups. As Figure 8 shown are the electron cloud distributions of the HOMO and LUMO of compounds 36-DBNM and DPNM. The target product has a good delocalized electron distribution in its LUMO energy level, while the electrons in its HOMO energy level are more confined to the linear main chain. The calculated HOMO and LUMO energy levels of 36-DBNM and DPNM are close to the experimental values.

[0051] Figure 9(a) An organic micro-nano crystal field effect transistor device was fabricated using compound 36-DBNM as the semiconductor layer. The device adopts a bottom-gate top-contact structure, with a nitrogen-doped silicon gate, gold source and drain electrodes, and a 300 nm thick silicon dioxide insulating layer. The surface of the silicon dioxide was modified with polystyrene to reduce surface defects. The organic micro-nano crystal field effect transistor device was characterized using a semiconductor parameter analyzer at room temperature. Figure 9 (b) shows the transfer characteristics curve of the device at room temperature, with an electron mobility of 5.43×10 -3 cm 2 V -1 s -1 , a threshold voltage of 44.5 V, and an on / off ratio of 10 3 , showing good air-stable field effect transistor characteristics. Figure 9 (c) An organic micro-nano crystal field effect transistor device was fabricated using compound DPNM as the semiconductor layer. The device adopts a bottom-gate top-contact structure, with a nitrogen-doped silicon gate, gold source and drain electrodes, and a 300 nm thick silicon dioxide insulating layer. The surface of the silicon dioxide was modified with polystyrene to reduce surface defects. The organic micro-nano crystal field effect transistor device was characterized using a semiconductor parameter analyzer at room temperature. Figure 9 (d) shows the transfer characteristics curve of the device at room temperature, with an electron mobility of 8.78×10 -3 cm 2 V -1 s -1 , a threshold voltage of 25.3 V, and an on / off ratio of 10 4 , showing good air-stable field effect transistor characteristics. Detailed implementation manners

[0052] The method of the present invention will be described in detail below.

[0053] In the present invention, unless otherwise specified, the equipment and raw materials used can be purchased from the market or are commonly used in the art.

[0054] Step 1: Preparation of amino compounds

[0055] 1a-1: Dissolve the amino-protected compound shown in Formula II and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir to carry out the reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 1. In the present invention, the palladium catalyst is preferably bis(triphenylphosphine)palladium dichloride; the molar ratio of the raw material compound, the R1-functionalized raw material compound and bis(triphenylphosphine)palladium dichloride is preferably 1:0.05 - 0.18, more preferably 1:0.09 - 0.12; the first organic solvent is preferably tetrahydrofuran, ethanol, dioxane or n-hexane, more preferably tetrahydrofuran; the first organic solvent is preferably a super-dry organic solvent; the dosage ratio of the first organic solvent to the raw material compound is preferably 10 - 100 mL:0.1 - 5 mmol, more preferably 30 - 50 mL:0.55 - 2.50 mmol, further preferably 30 - 50 mL:1.25 - 1.45 mmol; the reaction temperature is preferably 60 - 90 °C, more preferably 65 - 75 °C, further preferably 70 °C; the reaction time is preferably 8 - 17 h, more preferably 12 h; the reaction is preferably carried out under stirring conditions. After the reaction is completed, extract with dichloromethane, dry the obtained organic phase with anhydrous sodium sulfate, filter, remove the solvent in the obtained filtrate, carry out column chromatography separation, and evaporate the solvent in the obtained feed liquid under reduced pressure to obtain the R1-functionalized compound 1, which can be directly put into the next reaction.

[0056] 1a-2: Dissolve the R1-functionalized compound 1 obtained in 1a-1 in a second organic solvent, add lithium aluminum hydride as a reducing agent, stir at room temperature, and carry out a reduction reaction. After the reaction is completed, quench the reaction with a saturated NH4Cl solution, extract the organic phase with dichloromethane, separate the layers, dry, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the amino compound 1. In the present invention, the reducing agent is preferably lithium aluminum hydride; the molar ratio of the R1-functionalized compound to lithium aluminum hydride is preferably 1:6 to 15, more preferably 1:6 to 8; the second organic solvent is preferably tetrahydrofuran, ethanol, dioxane, or n-hexane, more preferably tetrahydrofuran; the second organic solvent is preferably an ultra-dry organic solvent; the dosage ratio of the second organic solvent to the raw material compound is preferably 10 to 100 mL: 0.3 to 4.35 mmol, more preferably 30 to 50 mL: 0.85 to 2.55 mmol, further preferably 30 to 50 mL: 1.38 to 1.43 mmol; the temperature of the reaction is preferably room temperature; the time of the reaction is preferably 5 to 9 h, more preferably 7 h; the reduction reaction is preferably carried out under stirring conditions. After the reduction reaction is completed, the present invention preferably quenches the reaction by adding a saturated ammonium chloride aqueous solution to the obtained system, extracts with dichloromethane, dries the obtained organic phase with anhydrous sodium sulfate, filters, removes the solvent from the obtained filtrate, carries out column chromatography separation, and evaporates the solvent from the obtained feed liquid under reduced pressure to obtain the amino compound 1, which can be directly put into the next reaction.

[0057] 1b-1: Dissolve the amino-protected compound represented by Formula III and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir to carry out the reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 2. In the present invention, the palladium catalyst is preferably bis(triphenylphosphine)palladium dichloride; the molar ratio of the raw material compound, the R1-functionalized raw material compound and bis(triphenylphosphine)palladium dichloride is preferably 1:0.05 - 0.18, more preferably 1:0.09 - 0.12; the first organic solvent is preferably tetrahydrofuran, ethanol, dioxane or n-hexane, more preferably tetrahydrofuran; the first organic solvent is preferably an ultra-dry organic solvent; the dosage ratio of the first organic solvent to the raw material compound is preferably 10 - 100 mL:0.1 - 5 mmol, more preferably 30 - 50 mL:0.55 - 2.50 mmol, further preferably 30 - 50 mL:1.25 - 1.45 mmol; the reaction temperature is preferably 60 - 90°C, more preferably 65 - 75°C, further preferably 70°C; the reaction time is preferably 8 - 17 h, more preferably 12 h; the reaction is preferably carried out under stirring conditions. After the reaction is completed, extract with dichloromethane, dry the obtained organic phase with anhydrous sodium sulfate, filter, remove the solvent in the obtained filtrate, carry out column chromatography separation, and evaporate the solvent in the obtained feed liquid under reduced pressure to obtain the R1-functionalized compound 2, which can be directly put into the next reaction.

[0058] 1b-2: Dissolve the R1-functionalized compound 2 obtained in 1b-1 in a second organic solvent, add trifluoroacetic acid, stir at room temperature for the deprotection reaction. After the reaction is completed, quench the reaction with saturated Na2CO3 solution, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain the crude product. The crude product is separated and purified by column chromatography to obtain the amino compound 2. In the present invention, the strong acid solvent is preferably trifluoroacetic acid; the molar ratio of the R1-functionalized compound to trifluoroacetic acid is preferably 1:5 to 11, more preferably 1:7 to 9; the second organic solvent is preferably dichloromethane, tetrahydrofuran, ethanol, dioxane or n-hexane, more preferably dichloromethane; the second organic solvent is preferably an ultra-dry organic solvent; the dosage ratio of the second organic solvent to the raw material compound is preferably 10 to 100 mL: 0.3 to 4.35 mmol, more preferably 30 to 50 mL: 0.85 to 2.55 mmol, further preferably 30 to 50 mL: 1.38 to 1.43 mmol; the temperature of the reaction is preferably room temperature; the time of the reaction is preferably 5 to 9 h, more preferably 7 h; the deprotection reaction is preferably carried out under stirring conditions. After the deprotection reaction is completed, the present invention preferably adds saturated sodium carbonate solution to the obtained system to quench the reaction, extracts with dichloromethane, dries the obtained organic phase with anhydrous sodium sulfate, filters, removes the solvent in the obtained filtrate, carries out column chromatography separation, and evaporates the solvent in the obtained feed liquid under reduced pressure to obtain the amino compound 2, which is directly put into the next reaction.

[0059] Step 2: Preparation of the functionalized indanone compound

[0060] In the present invention, ninhydrin, a compound containing an active methylene group, a catalyst and a third organic solvent are mixed to carry out a condensation reaction to obtain a functionalized indanone compound. In the present invention, the catalyst is preferably piperidine, pyridine or triethylamine, more preferably piperidine; the molar ratio of ninhydrin to the compound containing an active methylene group is preferably 1:1 to 3, more preferably 1:1.5 to 2; the molar ratio of ninhydrin to the catalyst is preferably 1:0.5 to 1, more preferably 1:0.7; the third organic solvent is preferably tetrahydrofuran, ethanol, dioxane, N,N-dimethylformamide or n-hexane, more preferably N,N-dimethylformamide; the third organic solvent is preferably an ultra-dry organic solvent; the dosage ratio of the third organic solvent to the raw material compound is preferably 10 to 100 mL: 0.2 to 6 mmol, more preferably 30 to 50 mL: 0.95 to 2.80 mmol, further preferably 30 to 50 mL: 1.45 to 1.65 mmol; the temperature of the reaction is preferably 70 to 100 °C, more preferably 85 to 95 °C, further preferably 90 °C; the time of the reaction is preferably 8 to 13 h, more preferably 10 h; the condensation reaction is preferably carried out under stirring conditions. After the condensation reaction is completed, extraction is carried out with dichloromethane, the obtained organic phase is dried with anhydrous sodium sulfate, filtered, the solvent in the obtained filtrate is removed, column chromatography separation is carried out, and the solvent in the obtained feed liquid is removed by reduced pressure evaporation to obtain an amino compound, which is directly put into the next reaction.

[0061] Step 3: Preparation of functionalized indanone-fused azabenzene

[0062] The amino compound 1 or amino compound 2 prepared in the above step 1 and the functionalized indanone compound prepared in step 2 are dissolved in a fourth organic solvent and mixed, and a condensation reaction is carried out to obtain a functionalized indanone-fused azabenzene. In the present invention, the molar ratio of the amino compound to the functionalized indanone compound is preferably 1:1 to 2, more preferably 1:1.1 to 1.3; the fourth organic solvent is preferably N,N-dimethylformamide, chloroform, toluene, dioxane, dimethyl sulfoxide or n-hexane, more preferably dimethyl sulfoxide; the fourth organic solvent is a common organic solvent; the dosage ratio of the fourth organic solvent to the raw material compound is preferably 10 to 100 mL: 0.4 to 6 mmol, more preferably 30 to 50 mL: 0.70 to 2.40 mmol, further preferably 30 to 50 mL: 1.20 to 1.40 mmol; the reaction temperature is preferably 100 to 130 °C, more preferably 110 to 120 °C, further preferably 115 °C; the reaction time is preferably 7 to 12 h, more preferably 9 h; the condensation reaction is preferably carried out under stirring conditions. After the condensation reaction is completed, extraction is carried out with dichloromethane, the obtained organic phase is dried with anhydrous sodium sulfate, filtered, the solvent in the obtained filtrate is removed, column chromatography separation is carried out, and the solvent in the obtained feed liquid is removed by evaporation under reduced pressure to obtain a functionalized indanone-fused azabenzene organic semiconductor material.

[0063] The technical solutions of the present invention will be further specifically described below through specific examples. It should be understood that the implementation of the present invention is not limited to the following examples, and any formal variation or change made to the present invention will fall within the protection scope of the present invention. In the present invention, unless otherwise specified, all parts and percentages are in units of amount of substance.

[0064] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0065] Example 1:

[0066] 1. Add compound S101 (1 eq), triisopropylsilylacetylene (5 eq), copper(I) iodide (5 eq), bis(triphenylphosphine)palladium(II) dichloride (0.1 eq), triethylamine (20 eq) and tetrahydrofuran into a flask containing a magnetic stirrer, and react at 70 °C. The reaction formula is as follows. After the reaction is completed, extraction is carried out with DCM, and then the organic phase is dried with anhydrous sodium sulfate. The organic phase is collected and evaporated to dryness, and separated and purified by column chromatography (DCM:PE = 1:8 → 1:2, V / V) to obtain product S102 (yield: 85%).

[0067]

[0068] 2. Add compound S102 (1 eq), lithium aluminum hydride (7 eq) and tetrahydrofuran into a flask containing a magnetic stir bar, and react at room temperature. The reaction equation is as follows. After the reaction is completed, slowly quench the reaction with saturated NH4Cl solution in an ice-water bath, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness. Purify by column chromatography (DCM:PE = 1:7 → 1:2, V / V) to obtain product S103 (yield: 72%).

[0069]

[0070] 3. Add ninhydrin hydrate (1 eq), malononitrile (1.7 eq), piperidine (0.7 eq) and DMF solution into a flask containing a magnetic stir bar, and react at 90 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness. Purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product S104 (yield: 73%).

[0071]

[0072] 4. Add compound S103 (1 eq), compound S104 (1.2 eq) and DMSO solution into a flask containing a magnetic stir bar, and react at 115 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness. Purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product 36-DBNM (yield: 68%).

[0073]

[0074] Example 2:

[0075] 1. Add compound S201 (1 eq), triisopropylsilylacetylene (5 eq), copper(I) iodide (5 eq), bis(triphenylphosphine)palladium(II) dichloride (0.1 eq), triethylamine (20 eq) and tetrahydrofuran into a flask containing a magnetic stir bar, and react at 70 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness. Purify by column chromatography (DCM:PE = 1:8 → 1:2, V / V) to obtain product S202 (yield: 85%).

[0076]

[0077] 2. Add compound S202 (1 eq), lithium aluminum hydride (7 eq) and tetrahydrofuran into a flask containing a magnetic stir bar, and react at room temperature. The reaction equation is as follows. After the reaction is completed, slowly quench the reaction with saturated NH4Cl solution in an ice-water bath, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and rotary evaporate it to dryness. Purify by column chromatography (DCM:PE = 1:7 → 1:2, V / V) to obtain product S203 (yield: 76%).

[0078]

[0079] 3. Add ninhydrin hydrate (1 eq), malononitrile (1.7 eq), piperidine (0.7 eq) and DMF solution into a flask containing a magnetic stir bar, and react at 90 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and rotary evaporate it to dryness. Purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product S104 (yield: 73%).

[0080]

[0081] 4. Add compound S203 (1 eq), compound S204 (1.2 eq) and DMSO solution into a flask containing a magnetic stir bar, and react at 115 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and rotary evaporate it to dryness. Purify by column chromatography (DCM:PE = 1:8 → 1:2, V / V) to obtain product DPNM (yield: 74%).

[0082]

[0083] Example 3:

[0084] 1. Add compound S301 (1 eq), phenylboronic acid (2.5 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), potassium carbonate and tetrahydrofuran into a flask containing a magnetic stir bar, and react at 70 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and rotary evaporate it to dryness. Purify by column chromatography (DCM:PE = 1:8 → 1:2, V / V) to obtain product S302 (yield: 70%).

[0085]

[0086] 2. Add compound S302 (1 eq), lithium aluminum hydride (7 eq) and tetrahydrofuran into a flask containing a magnetic stir bar, and react at room temperature. The reaction equation is as follows. After the reaction is completed, slowly quench the reaction with saturated NH4Cl solution in an ice-water bath, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:7 → 1:2, V / V) to obtain product S303 (yield: 79%).

[0087]

[0088] 3. Add ninhydrin hydrate (1 eq), malononitrile (1.7 eq), piperidine (0.7 eq) and DMF solution into a flask containing a magnetic stir bar, and react at 90 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product S304 (yield: 73%).

[0089]

[0090] 4. Add compound S303 (1 eq), compound S304 (1.2 eq) and DMSO solution into a flask containing a magnetic stir bar, and react at 115 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product 36-DTNM (yield: 74%).

[0091]

[0092] Example 4:

[0093] 1. Add compound S401 (1 eq), phenylboronic acid (2.5 eq), tetrakis(triphenylphosphine)palladium (0.1 eq), potassium carbonate and tetrahydrofuran into a flask containing a magnetic stir bar, and react at 70 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:8 → 1:2, V / V) to obtain product S402 (yield: 74%).

[0094]

[0095] 2. Add compound S402 (1 eq), lithium aluminum hydride (7 eq), and tetrahydrofuran to a flask containing a magnetic stir bar, and react at room temperature. The reaction equation is as follows. After the reaction is completed, quench the reaction slowly with saturated NH4Cl solution in an ice-water bath, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product S403 (yield: 67%).

[0096]

[0097] 3. Add ninhydrin hydrate (1 eq), malononitrile (1.7 eq), piperidine (0.7 eq), and DMF solution to a flask containing a magnetic stir bar, and react at 90 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:5 → 1:2, V / V) to obtain product S404 (yield: 64%).

[0098]

[0099] 4. Add compound S403 (1 eq), compound S404 (1.2 eq), and DMSO solution to a flask containing a magnetic stir bar, and react at 115 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:6 → 1:2, V / V) to obtain product DTNM (yield: 77%).

[0100]

[0101] Example 5:

[0102] 1. Add compound S501 (1 eq), triisopropylsilylacetylene (5 eq), copper(I) iodide (5 eq), bis(triphenylphosphine)palladium(II) dichloride (0.1 eq), triethylamine (20 eq), and tetrahydrofuran to a flask containing a magnetic stir bar, and react at 70 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:6 → 1:3, V / V) to obtain product S502 (yield: 68%).

[0103]

[0104] 2. Add compound S502 (1 eq), trifluoroacetic acid (8 eq) and dichloromethane into a flask containing a magnetic stir bar, and react at room temperature. The reaction equation is as follows. After the reaction is completed, slowly quench the reaction with saturated Na2CO3 solution in an ice-water bath, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:6 → 1:3, V / V) to obtain product S503 (yield: 64%).

[0105]

[0106] 3. Add ninhydrin hydrate (1 eq), malononitrile (1.7 eq), piperidine (0.7 eq) and DMF solution into a flask containing a magnetic stir bar, and react at 90 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:6 → 1:2, V / V) to obtain product S504 (yield: 63%).

[0107]

[0108] 4. Add compound S503 (1 eq), compound S504 (1.2 eq) and DMSO solution into a flask containing a magnetic stir bar, and react at 115 °C. The reaction equation is as follows. After the reaction is completed, extract with DCM, then dry the organic phase with anhydrous sodium sulfate, collect the organic phase and evaporate to dryness, and purify by column chromatography (DCM:PE = 1:6 → 1:2, V / V) to obtain product 36-DBNM (yield: 63%).

[0109]

[0110] The above are only preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention all fall within the scope of the technical solution of the present invention.

Claims

1. A functionalized indanone-fused azabenzene organic semiconductor material, characterized in that Its structural general formula is shown as the following formula Ⅰ: ； In the general formula: Ar represents any one of the following groups: ； R1 is selected from a hydrogen atom, a cyano group, a halogen group, an alkyl group, a silyl group, an alkoxy group or an aryl group.

2. The functionalized indanone-fused azabenzene organic semiconductor material according to claim 1, characterized in that: The halogen group is an iodine atom, a bromine atom, a chlorine atom or a fluorine atom; the alkyl group is a C1-C 40 linear alkyl group or a C3-C 40 branched alkyl group; the silyl group is (CH3)3SiC≡C*, (CH2CH3)3SiC≡C*, ((CH3)2CH)3SiC≡C*; the alkoxy group is -OR2, and R2 in the alkoxy group is a C1-C 40 linear alkyl group or a C3-C 40 branched alkyl group; the aryl group is benzene, naphthalene, anthracene, pyridine, pyrazine, quinoxaline or phenazine and their derivatives.

3. The preparation method of the functionalized indenone-fused azabenzanthrone according to claim 1, characterized in that It includes the following steps: Dissolve the amino compound and the functionalized indanone compound in a fourth organic solvent, heat and stir to carry out a condensation reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the functionalized indanone-fused azabenzene, that is, the target product shown in formula Ⅰ; The structure of the amino compound is shown as follows: ； The structure of the functionalized indanone compound is shown as follows: 。 4. The preparation method according to claim 3, characterized in that The amino compound is obtained by a method including the following steps: 1a-1: Dissolve the amino-protected compound shown in formula Ⅱ and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir to carry out a reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 1; The structure of the amino-protected compound shown in formula Ⅱ is shown as follows: ； Wherein: Ar' is selected from any one of the following groups: ； R3 is a hydrogen atom, a cyano group or a halogen group; The structure of the R1-functionalized compound 1 is shown as follows: ； 1a-2: Dissolve the R1-functionalized compound 1 obtained in 1a-1 in a second organic solvent, add lithium aluminum hydride as a reducing agent, stir at room temperature to carry out a reduction reaction. After the reaction is completed, quench the reaction with a saturated NH4Cl solution, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the amino compound; The structure of the amino compound is shown as follows: 。 5. The preparation method according to claim 3, characterized in that The amino compound is obtained by a method including the following steps: 1b-1: Dissolve the amino-protected compound shown in formula Ⅲ and the R1-functionalized raw material compound in a first organic solvent, add bis(triphenylphosphine)palladium dichloride as a catalyst, heat and stir to carry out a reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the R1-functionalized compound 2; The structure of the amino-protected compound shown in formula Ⅲ is shown as follows: ； Wherein: Ar' is selected from any one of the following groups: ； R3 is a hydrogen atom, a cyano group or a halogen group; The structure of the R1-functionalized compound 2 is shown as follows: ； 1b-2: Dissolve the R1-functionalized compound 2 obtained in 1b-1 in a second organic solvent, add trifluoroacetic acid, stir at room temperature to carry out a deprotection reaction. After the reaction is completed, quench the reaction with a saturated Na2CO3 solution, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain the amino compound; The structure of the amino compound is shown as follows: 。 6. The preparation method according to claim 3, characterized in that The functionalized indanone compound is obtained by a method including the following steps: Dissolve ninhydrin, malononitrile, and piperidine in a third organic solvent, heat and stir to carry out a condensation reaction. After the reaction is completed, extract the organic phase with dichloromethane, separate the liquid, dry it, and evaporate the solvent under reduced pressure to obtain a crude product. The crude product is separated and purified by column chromatography to obtain a functionalized indanone compound; The structure of the functionalized indanone compound is shown as follows: 。 7. Use of the functionalized indanone-fused azabenzene as defined in claim 1 as an organic semiconductor material in the preparation of an organic optoelectronic device.

8. The use according to claim 7, characterized in that: The organic optoelectronic device includes an organic field effect transistor, an organic light emitting diode, an organic photodetector, or an organic solar cell.

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