Acenaphthene derivatives and methods for their preparation, acenaphthene derivative materials and methods for their preparation and use

Abstract

The application relates to the field of organic photoelectric materials, and discloses a acenaphthene derivative, a preparation method of the acenaphthene derivative, an acenaphthene derivative material, a preparation method of the acenaphthene derivative material and application, the acenaphthene derivative has a structure shown in formula (1), wherein R1 and R2 are each independently selected from halogen atoms; R, R3, R4, R5 and R6 are each independently selected from hydrogen, halogen atoms, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, alkoxy or alkylthio. Based on the acenaphthene mother nucleus structure, halogen substituents and imide groups are introduced, the LUMO energy level of the compound can be effectively reduced, and through substitution reaction of the halogen, the further-prepared acenaphthene derivative material has good charge transport performance, is applied in a field effect transistor, and has the advantages of simple molecular structure, simple synthesis route and high mobility.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic optoelectronic materials, in particular to a acenaphthene derivative and a preparation method thereof, an acenaphthene derivative material and a preparation method and application thereof. BACKGROUND

[0002] Compared with inorganic semiconductor materials, organic semiconductor materials not only have the advantages of wider material sources, lower cost, and convenient processing, but also have good mechanical flexibility, and have wide application prospects in flexible electronic devices. Moreover, organic semiconductor materials, such as acenaphthene derivative materials, can be applied to the manufacture of solar cells, OLEDs and other devices, and their applications are also expanding with their development. According to the type of carrier transport, semiconductor materials are mainly divided into hole transport type (p-type), electron transport type (n-type) and bipolar type.

[0003] The acenaphthene nucleus can construct various functional molecular systems such as cardiacyclic alkenes and decacyclic alkenes. At present, there are many methods for preparing functional molecules by aromatic expansion of the benzene ring or double bond of acenaphthene, but the synthesis steps are long, the process is complex, and the yield is low (J. Am. Chem. Soc. 2019, 141, 1201; J. Am. Chem. Soc. 2015, 137, 1620; Angew. Chem. Int. Ed. 2013, 52, 5513). Substituted functionalization of the acenaphthene nucleus has the advantages of simple molecular structure and simple synthesis process, but there are few reports on non-aromatic expansion functionalization of the acenaphthene nucleus, and there are no reports on charge transport.

[0004] Therefore, it is necessary to further explore acenaphthene derivatives with good charge transport performance. SUMMARY

[0005] The purpose of the present application is to overcome the problems of poor charge transport performance, complex synthesis process and high cost in the prior art, and to provide an acenaphthene derivative and a preparation method thereof, an acenaphthene derivative material and a preparation method and application thereof. The acenaphthene derivative material has good charge transport performance and important application value in field effect transistors.

[0006] To achieve the above purpose, the first aspect of the present application provides an acenaphthene derivative, which has a structure shown in formula (1),

[0007]

[0008] wherein R1 and R2 are each independently selected from a halogen atom;

[0009] R, R3, R4, R5 and R6 are each independently selected from hydrogen, a halogen atom, a substituted or substituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group or an alkylthio group.

[0010] The second aspect of the present application provides a preparation method of the acenaphthene derivative, which comprises:

[0011] S1, subjecting an acenaphthene nucleus to a Friedel-Crafts acylation reaction;

[0012] S2, subjecting the product obtained in step S1 to a halogenation reaction, an acid anhydride reaction and an amidation reaction;

[0013] wherein the acenaphthene nucleus has a structure as shown in formula (2),

[0014]

[0015] wherein R3, R4, R5 and R6 have the same definitions as those in the first aspect.

[0016] The third aspect of the present application provides an acenaphthene derivative material, which is at least one of compounds having a structure as shown in formula (3);

[0017]

[0018] wherein R1' and R2' are each independently a cyano group or a C2-C10 dialkylamine group, and at least one of R1' and R2' is a cyano group;

[0019] R', R3', R4', R5' and R6' are each independently selected from hydrogen, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group or an alkylthio group.

[0020] The fourth aspect of the present application provides a preparation method of an acenaphthene derivative material, which comprises:

[0021] mixing the acenaphthene derivative, a cyanation solvent and a third solvent, and then performing a cyanation reaction;

[0022] wherein the amount of the cyanation reagent is 4-10 equivalents relative to 1 equivalent of the acenaphthene derivative.

[0023] The fifth aspect of the present application provides an acenaphthene derivative material prepared by the preparation method of the fourth aspect.

[0024] The sixth aspect of the present application provides a preparation method of an acenaphthene derivative material, which comprises:

[0025] Step B1, heating and refluxing a dialkylamine raw material; the dialkylamine raw material is at least one selected from N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-ethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide and N,N-diamylformamide.

[0026] Step B2, adding the acenaphthene derivative of the first aspect and a cyanating reagent to the product obtained in step B1 to react.

[0027] The seventh aspect of the present application provides the acenaphthene derivative material prepared by the above preparation method.

[0028] The eighth aspect of the present application provides the use of the acenaphthene derivative material of the third aspect, the fifth aspect or the seventh aspect in a field effect transistor.

[0029] The acenaphthene derivative provided by the present application can effectively reduce the LUMO energy level of the compound by introducing halogen substituents and imide groups based on the acenaphthene nucleus structure, and further prepared acenaphthene derivative materials have good charge transport performance through substitution reaction of halogen, and are applied in field effect transistors.

[0030] The preparation method of the acenaphthene derivative provided by the present application has the advantages of simplicity, high efficiency, low cost, high repeatability, high yield and high product purity.

[0031] The acenaphthene derivative material provided by the present application can effectively reduce or increase the electronic energy level of the compound by introducing imide, cyano or C2-C10 dialkylamine groups in the acenaphthene structure, and has good charge transport performance. When the structure of the acenaphthene derivative material has adjacent dialkylamine groups and cyano groups, the dialkylamine groups have electron-donating ability, the cyano groups have electron-withdrawing ability, the dialkylamine groups can undergo intramolecular charge transfer effect with the cyano groups, which helps to broaden the absorption spectrum, enhance the intermolecular interaction, and further improve the charge transport performance. When the structure of the acenaphthene derivative material has adjacent cyano groups, the acenaphthene derivative material has a lower electronic energy level and exhibits electron transport performance. The above-mentioned acenaphthene derivative material is applied in a field effect transistor, and has the advantages of good solubility, simple synthesis, easy processing and excellent charge mobility.

[0032] The preparation method of the acenaphthene derivative material provided by the present application can prepare the target product by using the acenaphthene derivative with high activity in liquid phase, and can introduce low-carbon dialkylamine (C2-C10) or raw materials that can produce low-carbon dialkylamine to introduce low-carbon dialkylamine groups. The reaction process is simple, without the need to directly add dialkylamine with foul odor and high toxicity, which greatly reduces the danger and complexity of the reaction conditions, and avoids the low efficiency caused by the gas-liquid two-phase reaction raw materials. BRIEF DESCRIPTION OF DRAWINGS

[0033] Figure 1 is the ultraviolet-visible absorption spectrum of the chloroform solution of the acenaphthene derivative material B1;

[0034] Figure 2The UV-Vis absorption spectrum of a chloroform solution of acenaphthene-derived material B2 is shown.

[0035] Figure 3 These are the cyclic voltammetry curves of acenaphthene-derived material B1;

[0036] Figure 4 These are the cyclic voltammetry curves for acenaphthene-derived material B2;

[0037] Figure 5 This is a schematic diagram of a field-effect transistor device.

[0038] Figure 6 These are the performance transfer curves of organic field-effect transistor devices containing acenaphthene-derived material B1;

[0039] Figure 7 These are the performance transfer curves of organic field-effect transistor devices containing acenaphthene-derived material B2. Detailed Implementation

[0040] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0041] The first aspect of the present invention provides an acenaphthene derivative having the structure shown in formula (1).

[0042]

[0043] R1 and R2 are each independently selected from halogen atoms;

[0044] R, R3, R4, R5, and R6 are each independently selected from hydrogen, halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, alkoxy groups, or alkylthio groups.

[0045] According to a specific embodiment of the present invention, R1 and R2 are each independently selected from fluorine, bromine or chlorine, more preferably bromine.

[0046] According to a specific embodiment of the present invention, the substituted or unsubstituted alkyl group is a straight-chain alkyl group or a branched alkyl group. Preferably, the substituted or unsubstituted alkyl group is a C1-C30 alkyl group, and more preferably a C1-C15 alkyl group, for example, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, etc. The substituent in the substituted alkyl group is preferably a halogen atom.

[0047] Preferably, the substituted or unsubstituted aryl group is a C6-C30 aryl group, and the substituent in the substituted aryl group is preferably a C1-C20 alkyl group or a halogen atom. For example, it includes, but is not limited to, phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-iso-propylphenyl, p-iso-propylphenyl, m-iso-propylphenyl, 1-naphthyl, 2-naphthyl, and the like.

[0048] Preferably, the number of carbon atoms in the alkylthio group is 1-30, preferably 1-20. For example, the alkylthio group includes, but is not limited to, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, and the like.

[0049] Preferably, the number of carbon atoms in the alkoxy group is 1-30, preferably 1-20. For example, the alkoxy group includes, but is not limited to, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, and the like.

[0050] According to a preferred embodiment of the present application, R is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, alkoxy or alkylthio; preferably methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-iso-propylphenyl, p-iso-propylphenyl, m-iso-propylphenyl, 1-naphthyl, 2-naphthyl, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy or decyloxy; R3, R4, R5, R6 are hydrogen.

[0051] The second aspect of the present application provides a preparation method of the acenaphthene derivative described above, which comprises:

[0052] S1, subjecting an acenaphthene nucleus to a Friedel-Crafts acylation reaction;

[0053] S2, subjecting the product obtained in step S1 to a halogenation reaction, an acid anhydride reaction and an amidation reaction;

[0054] wherein the acenaphthene nucleus has a structure as shown in formula (2),

[0055]

[0056] wherein R3, R4, R5, R6 are defined as the same as the definitions involved in the first aspect.

[0057] In the present application, the Friedel-Crafts acylation reaction refers to Friedel-Crafts acylation, and the conditions of the Friedel-Crafts acylation reaction in the present application are not particularly limited and can be carried out according to the conditions known in the art. For example, it can be carried out according to the method reported by Barattin, R et al. (Eur. J. Org. Chem. 2009, 2009, 1022-1026).

[0058] According to the present application, the structure of the product obtained after the acylation reaction of the acenaphthene nucleus can be represented as

[0059] In the present application, the sequence of the halogenation reaction, the anhydride reaction and the amidation reaction in step S2 can be adjusted according to the actual situation, for example, the halogenation reaction, the anhydride reaction and the amidation reaction can be carried out in sequence, or the anhydride reaction and the amidation reaction can be carried out first, and then the halogenation reaction, or the amidation reaction can be carried out first, and then the halogenation reaction and the anhydride reaction, preferably, the halogenation reaction, the anhydride reaction and the amidation reaction are carried out in sequence. Using the above preferred reaction route, it is beneficial to obtain better yield and more simple and safe reaction conditions.

[0060] According to the present application, the Friedel-Crafts acylation reaction, the halogenation reaction, the anhydride reaction and the amidation reaction can also independently include purifying the product obtained by the reaction. The purification can include one or a combination of several of the following ways: solid-liquid separation, washing, recrystallization, elution purification, etc., which can be selected by those skilled in the art according to the actual needs, and the present application does not have a particular limitation.

[0061] According to a preferred embodiment of the present application, the step S2 comprises:

[0062] S2-1, contacting the product obtained in step S1 with a halogenation reagent to carry out a halogenation reaction;

[0063] S2-2, contacting the product of the halogenation reaction with an acid to carry out an anhydride reaction;

[0064] S2-3, contacting the product of the anhydride reaction with an amine compound to carry out an amidation reaction;

[0065] wherein the general formula of the amine compound is R-NH2, and R is defined as the same as the definition involved in the first aspect.

[0066] The reaction route of this preferred embodiment can be represented as reaction formula (A):

[0067]

[0068] In the present application, the amine compound has a general formula of R-NH2, i.e. the amine compound can provide R group only. The selection of R has been described in detail in the foregoing, which will not be repeated here.

[0069] According to a specific embodiment of the present application, the halogenation reaction is bromination, fluorination or chlorination. The present application has a wide range of selection for the specific conditions of the halogenation reaction, as long as halogen substitution can be achieved. The amount of the halogenating agent can be selected according to the actual needs of the reaction.

[0070] According to a preferred embodiment of the present application, the halogenation reaction is bromination, and the conditions of the bromination reaction include: the reaction temperature is 70-100℃, for example, it can be 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃ or a range between specific temperatures.

[0071] Preferably, the reaction time is 1-10h, for example, it can be 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or the like.

[0072] In the present application, the selection of the halogenating agent is wide, as long as halogenation reaction can be achieved, and the conventional halogenating agent in the art can be applied to the present application, and the skilled in the art can select according to the needs of the reagent.

[0073] For example, when the halogenation reaction is bromination, the halogenating agent is preferably at least one of N-bromosuccinimide, liquid bromine, 1,3-dibromo-5,5-dimethylhydantoin, dibromo isocyanuric acid, 1,3,5-tribromo-1,3,5-triazine-2,4,6-trione, preferably N-bromosuccinimide and / or liquid bromine.

[0074] In the present application, preferably, the amount of the halogenating agent is 1-10 equivalents relative to 1 equivalent of the product obtained in step S1, for example, it can be any one of 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 or a range between two points. Preferably, the amount of the halogenating agent is 4-10 equivalents relative to 1 equivalent of the product obtained in step S1.

[0075] According to a specific embodiment of the present application, the preparation method further comprises: introducing an oxidation auxiliary agent in step S2-1, which is beneficial to obtaining unsaturated double bond while bromination. The oxidation auxiliary agent is preferably at least one of benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butyl alcohol peroxide, and tert-butyl perbenzoate, and is preferably benzoyl peroxide.

[0076] Preferably, the amount of the oxidation auxiliary agent is 0.01-1 equivalent, for example, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, etc., relative to 1 equivalent of the product obtained in step S1.

[0077] Preferably, the halogenation reaction is carried out in the presence of a first solvent.

[0078] In the present application, the specific type of the first solvent is not particularly limited, and a conventional organic solvent in the art can be used. Preferably, the first solvent is a halogenated hydrocarbon, and preferably, the halogenated hydrocarbon is at least one of monochloromethane, dichloromethane, trichloromethane, carbon tetrachloride, tetrachloroethane, 1-chloropropane, 2-chloropropane, chloro-n-butane, 2-chlorobutane, chloro-isobutane, chloro-sec-butane, chloro-tert-butane, n-bromopropane, bromo-isopropane, 1-bromobutane, and 2-bromobutane, and is preferably at least one of dichloromethane, trichloromethane, and carbon tetrachloride.

[0079] According to a specific embodiment of the present application, the temperature of the acid anhydridation reaction is 60-100℃, for example, 60℃, 62℃, 64℃, 66℃, 68℃, 70℃, 72℃, 74℃, 76℃, 78℃, 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃, etc., or a range between two specific temperature points.

[0080] Preferably, the time of the acid anhydridation reaction is 4-10h, for example, 4h, 5h, 6h, 7h, 8h, 9h, 10h, etc.

[0081] The present application has a wide range of choices for the acid, for example, the acid can be selected from inorganic acid and / or organic acid, and is preferably at least one of hydrochloric acid, hydrobromic acid, sulfuric acid, and acetic acid.

[0082] According to a specific embodiment of the present application, the amount of the acid is 12-100 equivalents relative to 1 equivalent of the product of the halogenation reaction.

[0083] In the present application, in order to ensure the full progress of the anhydridization reaction, preferably, the acid can be added in steps, the anhydridization reaction includes: after the product of the halogenation reaction is contacted with the first acid to carry out the anhydridization reaction for 3-4 h, the second acid is added to the reaction system, and the reaction is continued until the reaction is completed.

[0084] Preferably, the mass ratio of the second acid to the equivalent of the first acid is 0.5-1:1, for example, it can be 0.5:1, 0.55:1, 0.6:1, 0.65:1, 0.7:1, 0.75:1, 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, etc.

[0085] In the present application, the acid can come from an acid or an aqueous acid solution, when the acid is provided by an aqueous acid solution, the concentration of the aqueous acid solution can be 36-98wt%.

[0086] Preferably, the anhydridization reaction is carried out under stirring. The present application does not have special limitations on the conditions of the stirring, as long as it can promote the progress of the reaction.

[0087] According to a specific embodiment of the present application, the reaction temperature of the amidation reaction is 80-150℃, for example, it can be 80℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, etc. or a range between two specific temperature points.

[0088] Preferably, the reaction time of the amidation reaction is 36-60h, for example, it can be 36h, 38h, 40h, 42h, 44h, 46h, 48h, 50h, 52h, 54h, 56h, 58h, 60h, etc.

[0089] According to a preferred embodiment of the present application, the conditions of the amidation reaction include: first low-temperature reaction at 80-100℃ for 12-24h, and then high-temperature reaction at 110-140℃ for 12-48h; for example, the reaction temperature of the low-temperature reaction section can be 0℃, 82℃, 84℃, 86℃, 88℃, 90℃, 92℃, 94℃, 96℃, 98℃, 100℃, etc.; the reaction temperature of the high-temperature reaction section can be 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, etc.

[0090] According to a specific embodiment of the present application, the amidation reaction is carried out under a protective atmosphere, the protective atmosphere is preferably provided by at least one of nitrogen, argon and neon.

[0091] According to the present application, preferably, the amidation reaction is carried out in the presence of a second solvent, and the specific type of the second solvent is not particularly limited, and a conventional organic solvent in the art can be used. Preferably, the second solvent is an amide compound, for example, at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, and N,N-dimethylbutyramide.

[0092] The present application does not particularly limit the order of adding each material in the amidation reaction, and the product of the acid anhydridation reaction, the amine compound, and the second solvent can be mixed together in a reactor, or the second solvent can be added first, and then the product of the acid anhydridation reaction and the amine compound can be added.

[0093] According to a preferred embodiment of the present application, the amount of the amine compound is 1 to 3 equivalents, for example, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, or the like, relative to 1 equivalent of the product of the acid anhydridation reaction.

[0094] The third aspect of the present application provides a acenaphthene derivative material, which is at least one of compounds having a structure represented by formula (3);

[0095]

[0096] wherein R1' and R2' are each independently a cyano group or a C2-C10 dialkylamine group, and at least one of R1' and R2' is a cyano group;

[0097] R', R3', R4', R5', and R6' are each independently selected from hydrogen, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, or an alkylthio group.

[0098] In the present application, the carbon number of the C2-C10 dialkylamine group refers to the total number of carbons in the group.

[0099] According to the present application, in formula (3), at least one of R1' and R2' is a cyano group. For example, R1' and R2' can each be a cyano group, or R1' and R2' can be a cyano group and a dialkylamine group, respectively. Preferably, R1' and R2' are a cyano group and a dialkylamine group, respectively, and in the above preferred case, intramolecular charge transfer effects can occur between adjacent cyano groups and dialkylamine groups, which helps to further improve the charge transport performance.

[0100] According to the present application, preferably, R1' and R2' are each independently cyano or dimethylamine, and at least one of R1' and R2' is cyano.

[0101] According to a specific embodiment of the present application, the substituted or unsubstituted alkyl group is a linear alkyl group or a branched alkyl group, preferably, the substituted or unsubstituted alkyl group is a C1-C30 alkyl group, preferably a C1-C15 alkyl group, for example, including but not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, and the like, and the substituent in the substituted alkyl group is preferably a halogen atom.

[0102] Preferably, the substituted or unsubstituted aryl group is a C6-C30 aryl group, and the substituent in the substituted aryl group is preferably a C1-C20 alkyl group or a halogen atom. For example, including but not limited to phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-iso-propylphenyl, p-iso-propylphenyl, m-iso-propylphenyl, 1-naphthyl, or 2-naphthyl, and the like.

[0103] Preferably, the number of carbon atoms in the alkylthio group is 1-30, preferably 1-20, for example, the alkylthio group includes but is not limited to methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, and the like.

[0104] Preferably, the number of carbon atoms in the alkoxy group is 1-30, preferably 1-20, for example, the alkoxy group includes but is not limited to methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, and the like.

[0105] According to a preferred embodiment of the present application, R' is selected from a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, or an alkylthio group; preferably, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, iso-octyl, n-nonyl, phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-iso-propylphenyl, p-iso-propylphenyl, m-iso-propylphenyl, 1-naphthyl, 2-naphthyl, methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, or decyloxy; R3', R4', R5', R6' are hydrogen.

[0106] According to the present application, preferably, the optical band gap of the acenaphthene derivative material is not higher than 3 eV, preferably 1.5-3 eV, as measured by ultraviolet-visible absorption spectrum, and the optical band gap of acenaphthylene is about 3.59 eV, thus the acenaphthene derivative material provided by the present application has a narrower band gap and a wider absorption spectrum, which is conducive to absorbing visible light and preparing a visible light responsive optoelectronic device.

[0107] The present application provides a preparation method of the acenaphthene derivative material, which comprises mixing the acenaphthene derivative of the first aspect, a cyanation reagent and a third solvent, and then performing a cyanation reaction; wherein the amount of the cyanation reagent is 4-10 equivalents relative to 1 equivalent of the acenaphthene derivative.

[0108] It can be understood that the method can be used to prepare the compound having the structure as shown in formula (3) from the acenaphthene derivative having the structure as shown in formula (1) in one step, wherein R1' and R2' are both cyano, and the definitions of R, R', R3'-R6' and R3-R6 are the same.

[0109] The preparation method of the acenaphthene derivative material provided by the present application can be used to prepare the target product from the acenaphthene derivative having high activity in a liquid phase in one step.

[0110] In the present application, the selection range of the cyanation reagent is wide, as long as the cyanation reaction can be achieved, and the person skilled in the art can select according to the actual needs. Preferably, the cyanation reagent is selected from at least one of cuprous cyanide, zinc cyanide and potassium ferrocyanide.

[0111] According to the present application, preferably, the amount of the cyanation reagent is 4-10 equivalents relative to 1 equivalent of the acenaphthene derivative. For example, it can be 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10 and the like.

[0112] In the present application, the selection range of the third solvent is wide, as long as the uniform dissolution and mixing of the components can be achieved, and the person skilled in the art can select according to the actual needs. For example, it can be at least one of halogenated hydrocarbon, alkyl ketone, ether, aromatic hydrocarbon and organic amine.

[0113] Preferably, the halogenated hydrocarbon is selected from at least one of monochloromethane, dichloromethane, trichloromethane, tetrachloroethane, 1-chloropropane, 2-chloropropane, chloro-n-butane, 2-chlorobutane, chloroisobutane, chloro-sec-butane, chloro-tert-butane, n-bromopropane, bromo-isopropyl, 1-bromobutane and 2-bromobutane, and preferably at least one of dichloromethane, trichloromethane and tetrachloroethane.

[0114] Preferably, the ether is at least one selected from the group consisting of tetrahydrofuran, methyl ethyl ether, diethyl ether, n-propyl ether, isopropyl ether, n-butyl ether, ethyl butyl ether, ethylene glycol dimethyl ether, ethylene oxide, methyl tert-butyl ether and ethyl tert-butyl ether.

[0115] Preferably, the aromatic hydrocarbon can be a substituted or unsubstituted aromatic hydrocarbon, for example, can be at least one selected from the group consisting of benzene, toluene, xylene and chlorobenzene.

[0116] Preferably, the alkyl ketone can be at least one selected from the group consisting of N-methyl pyrrolidone and / or N-ethyl pyrrolidone.

[0117] Preferably, the organic amine can be at least one selected from the group consisting of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide and N,N-dimethylbutyramide.

[0118] According to a most preferred embodiment of the present application, the third solvent is N-methyl pyrrolidone and / or N-ethyl pyrrolidone.

[0119] According to a specific embodiment of the present application, the temperature of the cyanation reaction is 100-200℃, for example, can be 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, or a range between any two of the specific temperature points.

[0120] Preferably, the time of the cyanation reaction is 8-48h. For example, the cyanation reaction time can be 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, or a specific reaction time.

[0121] According to a preferred embodiment of the present application, the cyanation reaction is carried out under a protective atmosphere, which is preferably provided by at least one of nitrogen, argon and neon.

[0122] Preferably, the contacting is carried out under stirring. The present application does not have a particular limitation on the conditions of the stirring as long as it can promote the reaction.

[0123] In the present application, preferably, the preparation method further comprises purifying the product of the cyanation reaction. The purification can be performed using a method conventional in the art, which can be selected by those skilled in the art according to actual conditions. For example, the purification can be performed using a column chromatography system. The present application does not have particular limitations on the conditions and solvents of the column chromatography system. For example, the solvent used in the column chromatography can be a mixture of dichloromethane and petroleum ether, and the volume ratio of dichloromethane to petroleum ether is preferably 1:5-5:1.

[0124] The fifth aspect of the present application provides acenaphthene derivative materials prepared by the above preparation method. The acenaphthene derivative materials have low electronic energy levels and good charge transport properties, and have the characteristics of N-type semiconductors.

[0125] The structure of the acenaphthene derivative material can be represented as

[0126] wherein R', R3', R4', R5', and R6' are each independently selected from hydrogen, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, an alkoxy group, or an alkylthio group.

[0127] The sixth aspect of the present application provides a preparation method of an acenaphthene derivative material, which comprises:

[0128] Step B1, heating and refluxing a dialkylamine raw material; the dialkylamine raw material is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-ethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, and N,N-diamylformamide;

[0129] Step B2, adding the acenaphthene derivative of the first aspect and a cyanation reagent to the product obtained in step B1, and performing a reaction.

[0130] The method can prepare a compound having a structure as shown in formula (3) from an acenaphthene derivative having a structure as shown in formula (1), where R1' and R2' are a cyano group and a C2-C10 dialkylamine group, respectively, and R and R', R3'-R6' and R3-R6 have the same definitions as R and R', R3-R6, respectively.

[0131] According to the present application, the dialkylamine is generated by heating the dialkylamine raw material in step B1. The inventors of the present application have found in their research that, by using a compound containing or capable of generating dialkylamine, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-ethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, N,N-diamylformamide, etc., as the dialkylamine raw material, and by introducing the dialkylamine group through the dialkylamine generated by heating and refluxing, the reaction process is simple, the direct addition of the foul-smelling and toxic dialkylamine gas phase is avoided, the risk of the reaction conditions and the complexity of the operation are greatly reduced, and the low efficiency caused by the reaction raw material being in the gas-liquid two-phase state is avoided.

[0132] The inventors of the present application have also found in their research that, when the above dialkylamine raw material and the cyanating agent are heated in the solution at the same time, it is difficult to provide the dialkylamine, which is presumably because the presence of the cyanating agent hinders the decomposition of the dialkylamine raw material. Therefore, the dialkylamine raw material needs to be heated and refluxed first. At the same time, it can be understood that the undecomposed part of the dialkylamine raw material can play the role of a solvent in step B2.

[0133] Preferably, the amount of the dialkylamine raw material is 20-40 equivalents relative to 1 equivalent of the acenaphthene derivative. For example, it can be 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, etc.

[0134] In the present application, the selection range of the cyanating agent is wide, as long as the cyanation reaction can be achieved, and the person skilled in the art can select according to the actual needs. Preferably, the cyanating agent is at least one selected from cuprous cyanide, zinc cyanide, and potassium ferrocyanide.

[0135] In the present application, preferably, the amount of the cyanating agent is 4-30 equivalents relative to 1 equivalent of the acenaphthene derivative. For example, it can be 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, etc. The inventors of the present application have found in their research that, when the amount of the cyanating agent is low, the yield is low, which is presumably caused by the competitive effect of the cyanating agent and the dialkylamine. In order to further improve the yield, preferably, the amount of the cyanating agent is 11-30 equivalents relative to 1 equivalent of the acenaphthene derivative.

[0136] In the present application, preferably, in step B1, the heating temperature is 100-200℃; for example, it can be 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, or a range between any two of the above-mentioned temperature points.

[0137] Preferably, the refluxing time is 1-4h; for example, it can be 1h, 1.5h, 2h, 2.5h, 3.5h, 4h, or the like.

[0138] Preferably, in step B2, the reaction conditions include: the temperature is 100-200℃; for example, it can be 100℃, 105℃, 110℃, 115℃, 120℃, 125℃, 130℃, 135℃, 140℃, 145℃, 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, or a range between any two of the above-mentioned temperature points.

[0139] Preferably, the reaction time is 12-48h. For example, the reaction time can be 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h, 38h, 40h, 42h, 44h, 46h, 48h, or the like.

[0140] According to a preferred embodiment of the present application, the cyanation reaction is carried out under a protective atmosphere, which is preferably provided by at least one of nitrogen, argon and neon.

[0141] Preferably, the reaction is carried out under stirring. The present application does not have any particular limitation on the stirring condition, as long as it can promote the reaction.

[0142] In the present application, preferably, the preparation method further comprises: purifying the product of the reaction in step B2. The purification can be carried out by using conventional methods in the art, for example, it can be carried out by using a silica gel column.

[0143] The seventh aspect of the present application provides a acenaphthene derivative material prepared by the above-mentioned preparation method.

[0144] The structure of the acenaphthene derivative material is selected from formula (i) and / or formula (ii),

[0145]

[0146] R', R3', R4', R5', and R6' are each independently selected from hydrogen, halogen atoms, substituted or substituted alkyl groups, substituted or unsubstituted aryl groups, alkoxy groups, or alkylthio groups, and n = 1, 1, 2, 3, and 4.

[0147] The acenaphthene-derived material has a low electronic energy level and good charge transport performance, exhibiting characteristics of a P-type semiconductor.

[0148] The eighth aspect of the present invention provides the application of the acenaphthene-derived materials described in the third, fifth or seventh aspects in field-effect transistors.

[0149] The present invention will be described in detail below through embodiments.

[0150] Unless otherwise specified, all raw materials used in the following embodiments are commercially available.

[0151] In the following examples, the structure of the products of each step was determined by 1H NMR spectroscopy.

[0152] In the following examples, room temperature refers to 25±5℃.

[0153] In the following examples, the yield (%) of each step is calculated as (actual yield / theoretical yield) × 100%.

[0154] The following examples illustrate the preparation of acenaphthene derivatives.

[0155] Example A1

[0156] S1, with acenaphthene nucleus Using the raw materials, Friedel-Crafts acylation was carried out according to the method described in the literature Barattin, R.; Gourdon, A. Eur. J. Org. Chem. 2009, 1022–1026.

[0157] S2-1. 8.88 g (30.0 mmol, 1 eq) of the product obtained in step S1 was placed in a 250 mL inclined two-necked flask, and 75 mL of carbon tetrachloride was added. The mixture was heated and stirred at 50 °C until a homogeneous solution was obtained. 32.04 g (180.0 mmol, 6 eq) of N-bromosuccinimide and 0.729 g (3.0 mmol, 0.1 eq) of benzoyl peroxide were added to the above solution to initiate a bromination reaction. The mixture was heated to 80 °C and refluxed with stirring for 4 hours. After the reaction was complete, the solution was extracted with dichloromethane, and the organic phase was washed with saturated sodium thiosulfate aqueous solution and water. The bromination product was purified by silica gel column chromatography using ethyl acetate as the eluent. The product was a yellow solid, weighing 2.6 g, with a yield of 20%.

[0158] The structure of the product was confirmed by 1H NMR spectroscopy: MS (MALDI-TOF): 436.98; 1H NMR (400 MHz, Chloroform-d) δ 7.63 (d, J = 7.1 Hz, 2H), 7.43 (d, J = 7.1 Hz, 2H), 3.09 (s, 3H), 2.87 (s, 3H).

[0159] S2-2, 2.25 g (5 mmol, 1 eq) of the above bromination reaction product was added to a 100 mL conical flask, 21 mL of concentrated hydrochloric acid (mass concentration of 36-38 wt%, 50.4 eq) was added, heated to 70°C, heated and stirred for 3 h, 10 mL of concentrated hydrochloric acid was added, and the reaction was continued at 70°C for 4 h. After the heating was completed, the flask was placed in an ice water bath, then suction filtration was taken to precipitate, and washed with a large amount of water, and the anhydride reaction product was obtained as a dark red solid after recrystallization with chloroform, weighing 0.675 g, with a yield of 35%.

[0160] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 379.86; 1 H NMR (400 MHz, Chloroform-d) δ 8.50 (d, J = 7.2 Hz, 2H), 7.84 (d, J = 7.2 Hz, 2H).

[0161] S2-3, 0.379 g (1 mmol, 1 eq) of the anhydride reaction product was added to a 25 mL conical flask, 0.155 g (1.2 mmol, 1.2 eq) of n-octylamine, and 5 mL of DMF were added. Under a nitrogen atmosphere, the reaction was carried out at 90°C for 12 hours, followed by heating to 110°C, and the reaction was continued for 12 hours. The solution was extracted with dichloromethane, and the organic phase was washed with water. The amide reaction product was obtained as a dark red solid after purification by silica gel column with dichloromethane as the eluent, weighing 0.328 g, with a yield of 67%.

[0162] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 491.02; 1 H NMR (400 MHz, Chloroform-d) δ 8.35 (d, J = 7.2 Hz, 2H), 7.70 (d, J = 7.2 Hz, 2H), 4.16-4.08 (t, 2H), 1.55 (p, 2H), 1.32-1.25 (m, 8H), 0.87 (m, J = 6.1, 5.6, 3.3 Hz, 3H), which proved that the structure of the acenaphthene derivative obtained was as shown in formula (1), wherein R is n-octyl, R1 and R2 are bromine atoms, R3, R4, R5, R6 are hydrogen, and the acenaphthene derivative is denoted as A1.

[0163] Example A2

[0164] According to the method of Example A1, except that step S2-3 comprises:

[0165] 0.379 g (1 mmol, 1 eq) of the anhydride reaction product was added to a 38 mL pressurized reaction tube, along with 0.088 g (1.2 mmol, 1.2 eq) of n-butylamine and 15 mL of glacial acetic acid. The reaction was carried out at 112 °C for 12 hours under a nitrogen atmosphere. The solution was extracted with dichloromethane, and the organic phase was washed with water. The amidation product was obtained by silica gel column chromatography using dichloromethane as the eluent; it was a dark red solid weighing 0.185 g, with a yield of 42%.

[0166] The structure of the product was confirmed by 1H NMR spectroscopy: MS (MALDI-TOF): 434.94; 1 ¹H NMR (400MHz, Chloroform-d) δ 8.28 (d, J = 7.5Hz, 2H), 8.00 (d, J = 7.5Hz, 2H), 3.46 (t, J = 7.1Hz, 2H), 1.65 (p, J = 7.1Hz, 2H), 1.41–1.30 (m, 2H), 0.96 (t, J = 8.0Hz, 3H), proving that the structure of the obtained acenaphthene derivative is as shown in formula (1), where R is n-butyl, R1 and R2 are bromine atoms, and R3, R4, R5, and R6 are hydrogen atoms. This acenaphthene derivative is denoted as A2.

[0167] Example A3

[0168] S1, with acenaphthene nucleus Using the raw materials, Friedel-Crafts acylation was carried out according to the method described in the literature Barattin, R.; Gourdon, A. Eur. J. Org. Chem. 2009, 1022–1026.

[0169] S2-1. Add 2 g (6.75 mmol, 1 eq) of the product obtained in step S1 to a 100 mL inclined two-necked flask, add 5 mL of concentrated hydrochloric acid (36-38 wt%, 68.04 eq), heat to 70 °C, and stir for 5 h. Add another 5 mL of concentrated hydrochloric acid and continue the reaction at 70 °C for 4 h. After heating is complete, place the two-necked flask in an ice-water bath, then filter to collect the precipitate, wash with plenty of water, and recrystallize from acetic anhydride solution to obtain the anhydride reaction product, weighing 0.68 g, yield 39%.

[0170] The structure of the product was confirmed by 1H NMR spectroscopy: MS (MALDI-TOF): 224.01; 1 H NMR (400MHz, Chloroform-d) δ8.54 (d, 2H, 3J = 7.0Hz, Np), δ7.65 (d, 2H, 3J = 7.0Hz, Np), δ3.45ppm (s, 4H, CH2).

[0171] S2-2, 2.24 g (10 mmol, 1 eq) of the reaction product of S2-1 was added to a 250 mL conical flask, 100 mL of carbon tetrachloride was added, and heated and stirred at 50°C to a homogeneous solution. To the above solution, 10.6 g (60 mmol, 6 eq) of N-bromosuccinimide and 0.24 g (1 mmol, 0.1 eq) of benzoyl peroxide were added to carry out bromination reaction, heated to 80°C and stirred to reflux for 4 hours. After the reaction was completed, the red precipitate was filtered and washed with a large amount of sodium bicarbonate solution and deionized water. Then recrystallized with chloroform to obtain the bromination product as a red solid, 405.5 mg, yield 10.6%.

[0172] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 379.86; 1 H NMR (400 MHz, Chloroform-d) δ 8.50 (d, J = 7.2 Hz, 2H), 7.84 (d, J = 7.2 Hz, 2H).

[0173] S2-3, 0.379 g (1 mmol, 1 eq) of the product obtained in S2-2 was added to a 25 mL conical flask, 0.155 g (1.2 mmol, 1.2 eq) of n-octylamine, and 5 mL of DMF were added. Under nitrogen atmosphere, 90°C for 12 hours, followed by heating to 110°C, continue to react for 12 hours. The solution was extracted with dichloromethane, and the organic phase was washed with water. The amide reaction product was obtained by silica gel column purification with dichloromethane as eluent, as a dark red solid, 0.328 g, yield 67%.

[0174] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 491.02; 1 H NMR (400 MHz, Chloroform-d) δ 8.35 (d, J = 7.2 Hz, 2H), 7.70 (d, J = 7.2 Hz, 2H), 4.16-4.08 (t, 2H), 1.55 (p, 2H), 1.32-1.25 (m, 10H), 0.87 (m, J = 6.1, 5.6, 3.3 Hz, 3H), which proved that the structure of the obtained acenaphthene derivative was as shown in formula (1), wherein R was n-octyl, R1 and R2 were bromine atoms, R3, R4, R5, R6 were hydrogen, and the acenaphthene derivative was denoted as A3.

[0175] In this example, the acid anhydridation reaction was carried out first, followed by the halogenation reaction, and the product of the halogenation reaction was subjected to amidation. The reaction sequence was changed, and the target product was also prepared, and the yield of the product was slightly lower than that of Example A1.

[0176] Example A4

[0177] S1, acenaphthene nucleus as raw material, Friedel-Crafts acylation reaction according to the method of literature Barattin, R.; Gourdon, A. Eur. J. Org. Chem. 2009, 2009, 1022-1026.

[0178] S2-1, 17.76 g (60.0 mmol, 1 eq) of the product obtained in step S1 was placed in a 1000 mL conical flask, 150 mL of carbon tetrachloride was added, and heated to 50°C to obtain a uniform solution. To the above solution, 64.08 g (360.0 mmol, 6 eq) of N-bromosuccinimide and 1.458 g (6.0 mmol, 0.1 eq) of benzoyl peroxide were added to carry out the bromination reaction, and heated to 80°C to stir and reflux for 4 hours. After the reaction was completed, the solution was extracted with dichloromethane, and the organic phase was washed with saturated aqueous sodium thiosulfate and water. The bromination reaction product was obtained as a yellow solid by silica gel column purification with ethyl acetate as the eluent, weighing 5.2 g, with a yield of 20%.

[0179] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 436.98; 1 H NMR (400 MHz, Chloroform-d) δ 7.63 (d, J = 7.1 Hz, 2H), 7.43 (d, J = 7.1 Hz, 2H), 3.09 (s, 3H), 2.87 (s, 3H).

[0180] S2-2, 4.5 g (10 mmol, 1 eq) of the above bromination reaction product was added to a 250 mL conical flask, 42 mL of concentrated hydrochloric acid (mass concentration of 36-38 wt%, 50.4 eq) was added, heated to 70°C, heated and stirred for 3h, 10 mL of concentrated hydrochloric acid was added, and the reaction was continued at 70°C for 4h. After the heating was completed, the conical flask was placed in an ice water bath, then suction filtration was taken to obtain the precipitate, and washed with a large amount of water, and the anhydride reaction product was obtained as a dark red solid by recrystallization with chloroform, weighing 1.35 g, with a yield of 35%.

[0181] S2-3, 1.137 g (3 mmol, 1 eq) of the anhydride reaction product was added to a 100 mL conical flask, 0.335 g (3.6 mmol, 1.2 eq) of aniline and 25 mL of DMF were added. Under a nitrogen atmosphere, the reaction was carried out at 90°C for 12 hours, followed by heating to 110°C, and the reaction was continued for 12 hours. The solution was extracted with dichloromethane, and the organic phase was washed with water. The amide reaction product was obtained as a dark red solid by silica gel column purification with dichloromethane as the eluent, weighing 0.525 g, with a yield of 32%.

[0182] ​The structure of the product was confirmed by1H NMR. MS (MALDI-TOF): 436.98; 1 H NMR (400 MHz, Chloroform-d) δ 8.39 (d, J = 7.5 Hz, 2H), 8.03 (d, J = 7.5 Hz, 2H), 7.50-7.43 (m, 2H), 7.46-7.38 (m, 3H), confirming that the structure of the acenaphthene derivative obtained is as shown in formula (1), wherein R is a phenyl group, R1and R2are bromine atoms, R3, R4, R5, R6are hydrogen, which is designated as A4.

[0183] Example A5

[0184] According to the method of Example A4, except that step S2-3 comprises: adding 1.137 g (3 mmol, 1 eq) of the acid anhydridation reaction product into a 100 mL slanting two-necked flask, adding 0.639 g (3.6 mmol, 1.2 eq) of 2,6-diisopropylaniline, 25 mL of DMF. Under a nitrogen atmosphere, 90 °C for 12 hours, followed by warming to 110 °C, continue to react for 12 hours. Extract the solution with dichloromethane, wash the organic phase with water. Purify the amide reaction product by silica gel column with dichloromethane as eluent to obtain a dark red solid, 0.836 g, yield 51%.

[0185] The structure of the product was confirmed by1H NMR. MS (MALDI-TOF): 436.98; 1 H NMR (400 MHz, Chloroform-d) δ 8.41 (d, J = 7.5 Hz, 2H), 8.04 (d, J = 7.5 Hz, 2H), 7.26 (dd, J = 8.1, 6.7 Hz, 1H), 7.18 (dd, J = 7.4, 0.8 Hz, 2H), 3.18-3.06 (m, 2H), 1.19 (d, J = 6.8 Hz, 12H), confirming that the structure of the acenaphthene derivative obtained is as shown in formula (1), wherein R is a 2,6-diisopropylphenyl group, R1and R2are bromine atoms, R3, R4, R5, R6are hydrogen, which is designated as A5.

[0186] Example A6

[0187] According to the method of Example A4, except that step S2-3 comprises: adding 1.137 g (3 mmol, 1 eq) of the acid anhydridation reaction product into a 38 mL pressurized reaction tube, adding 6 mL of ethanol, 7.5 mL of ammonia water. Under a nitrogen atmosphere, 70 °C for 12 hours, cool to room temperature, filter, wash with n-hexane, 0.66 g of red solid, yield 61%.

[0188] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 378.85; 1 H NMR (400 MHz, Chloroform-d) δ 8.33 (d, J = 7.5 Hz, 2H), 8.01 (d, J = 7.5 Hz, 2H), which proved that the structure of the obtained acenaphthene derivative was as shown in formula (1), wherein R was a hydrogen atom, R1and R2were bromine atoms, R3, R4, R5, R6were hydrogens, and the acenaphthene derivative was recorded as A6.

[0189] The following examples are used to illustrate the preparation of acenaphthene derivative materials.

[0190] Example B1

[0191] 0.172 g (1.92 mmol, 4.8 eq) of cuprous cyanide was weighed into a reaction tube, 2 mL (2.056 g) of N-methylpyrrolidone was added, and after stirring and heating to 160°C under a nitrogen atmosphere, 200 mg (0.40 mmol, 1 eq) of acenaphthene derivative A1 was added, and the reaction was continued at 160°C for 9 h. The solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by silica gel column chromatography with dichloromethane: petroleum ether = 1:1 as eluent, and acenaphthene derivative B1 was obtained as an orange yellow solid, weighing 0.032 g, with a calculated yield of 21%.

[0192] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 383.20 1 H NMR (400 MHz, Chloroform-d) δ 8.61 (d, J = 7.3 Hz, 2H), 8.29 (d, J = 7.3 Hz, 2H), 4.18 (t, J = 7.7 Hz, 2H), 1.72 (q, J = 7.0 Hz, 2H), 1.30 (s, 10H), 0.94-0.86 (m, 3H), which proved that the prepared acenaphthene derivative B1 had a structure as shown in formula (3), wherein R1’ and R2’ were cyano groups, R3’, R4’, R5’, R6’ were hydrogens, and R’ was a n-octyl group.

[0193] Figure 1 The UV-Vis absorption spectrum of a chloroform solution (10 -5 M) of B1 was measured. As can be seen from the figure, the compound exhibited three main absorption peaks at 242, 385, and 407 nm, and the optical band gap was calculated to be 2.79 eV.

[0194] Electrochemical property tests were performed using a three-electrode system: a glassy carbon single electrode as the working electrode, a platinum wire as the counter electrode, Ag / AgCl as the reference electrode, and tetrabutylammonium hexafluorophosphate as the electrolyte.

[0195] Figure 3The cyclic voltammogram of B1 was tested under the condition of -2.5-1.0V and the scanning rate of 100mV / s. The initial oxidation potential was 0.60V and the reduction potential was -0.64V. The LUMO was calculated to be -4.16eV and the HOMO was calculated to be -6.95eV by the band gap. It was shown that the introduction of cyano group significantly reduced the LUMO energy level of the compound.

[0196] Example B2

[0197] 2mL (25eq) of N,N-dimethylformamide was added to the reaction tube, and after stirring and heating to 160°C under nitrogen atmosphere, 0.574g (6.4mmol, 16eq) of cuprous cyanide and 200mg (0.40mmol, 1eq) of acenaphthene derivative A1 were added, and the reaction was continued to reflux at 160°C for 18 hours. After the reaction was completed, the temperature was returned to room temperature, and the solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by silica gel column chromatography using dichloromethane as the eluent, and acenaphthene derivative B2 was obtained as a blue solid, weighing 0.063g, with a calculated yield of 32%.

[0198] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 401.21 1 H NMR (400 MHz, Chloroform-d) δ 8.39 (dd, J = 25.1, 7.5 Hz, 4H), 8.02 (d, J = 7.6 Hz, 2H), 7.43 (d, J = 7.4 Hz, 2H), 4.21-4.09 (m, 2H), 1.72 (p, J = 7.5 Hz, 2H), 1.49-1.20 (m, 10H), 0.89 (t, J = 6.2 Hz, 3H). It was proved that the acenaphthene derivative B2 prepared had the structure shown in formula (3), wherein R1’ was cyano, R2’ was dimethylamino, R3’, R4’, R5’, R6’ were hydrogen, and R’ was n-octyl.

[0199] Figure 2 The UV-Vis absorption spectrum of the chloroform solution (10 -5 M) of B2 was measured. As can be seen from the figure, the compound showed two main absorption peaks at 231nm and 253nm, and an electronic transfer absorption peak at 600nm, and the optical band gap was 1.68eV.

[0200] Figure 4The cyclic voltammogram of B2 was obtained under the conditions of -2.5-1.0 V and a scan rate of 100 mV / s. The initial oxidation potential was 0.65 V, and the reduction potential was -0.51 V. The LUMO was calculated to be -3.42 eV, and the HOMO was calculated to be -5.10 eV by the band gap. The introduction of the cyano group reduced the LUMO energy level of the compound, and the narrow band gap made the compound have the potential to be a bipolar material.

[0201] Example B3

[0202] 2 mL (25 eq) of N,N-dimethylformamide was added to the reaction tube, and after stirring and heating to 160°C under a nitrogen atmosphere, it was refluxed for 4 hours. Then 0.574 g (6.4 mmol, 16 eq) of cuprous cyanide and 200 mg (0.40 mmol, 1 eq) of acenaphthene derivative A1 were added, and the reaction was continued to reflux at 160°C for 18 hours. After the reaction was completed, it was cooled to room temperature, and the solution was extracted with dichloromethane. The organic phase was washed with brine. Purification was performed on a silica gel column with dichloromethane as the eluent to obtain acenaphthene derivative B3.

[0203] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 491.02; 1 H NMR (400 MHz, CDCl3 / DMSO) δ 7.95 (d, J = 7.5 Hz, 2H), 7.88 (d, J = 7.5 Hz, 2H), 3.45 (t, J = 7.1 Hz, 2H), 1.63 (p, J = 7.1 Hz, 2H), 1.41-1.30 (m, 2H), 0.96 (t, J = 8.0 Hz, 3H), which proved that the acenaphthene derivative B2 prepared had the structure shown in formula (3), wherein R1’ was cyano, R2’ was diethylamino, R3’, R4’, R5’, R6’ were hydrogen, and R’ was n-octyl.

[0204] Example B4

[0205] 2 mL (25 eq) of N,N-dimethylformamide was added to the reaction tube, and after stirring and heating to 160°C under a nitrogen atmosphere, it was refluxed for 4 hours. Then 0.574 g (6.4 mmol, 16 eq) of cuprous cyanide and 200 mg (0.40 mmol, 1 eq) of acenaphthene derivative A1 were added, and the reaction was continued to reflux at 160°C for 18 hours. After the reaction was completed, it was cooled to room temperature, and the solution was extracted with dichloromethane. The organic phase was washed with brine. Purification was performed on a silica gel column with dichloromethane as the eluent to obtain acenaphthene derivative B3.

[0206] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 491.02; 1H NMR (400 MHz, Chloroform-d) δ 8.42 (d, J = 7.5 Hz, 1H), 8.29 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.51 - 7.38 (m, 5H), 3.03 (s, 6H), confirming that the acenaphthene derivative B4 prepared has the structure shown in formula (3), wherein R1' is cyano, R2' is dimethylamine, R3', R4', R5', R6' are hydrogen, R' is phenyl.

[0207] Example B5

[0208] Into a reaction tube, 0.172 g (1.92 mmol, 4.8 eq) of cuprous cyanide was weighed, 2 mL (2.056 g) of N-methylpyrrolidone was added, after stirring and heating to 160 °C under nitrogen atmosphere, 182 mg (0.40 mmol, 1 eq) of acenaphthene derivative A4 was added, and the reaction was continued at 160 °C for 9 h. The solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by silica gel column chromatography with dichloromethane: petroleum ether = 1 : 1 as eluent, and acenaphthene derivative B5 was obtained as an orange solid, weighing 0.034 g, with a calculated yield of 24%.

[0209] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 347.07 1 H NMR (400 MHz, Chloroform-d) δ 8.42 (d, J = 7.5 Hz, 1H), 8.29 (d, J = 7.5 Hz, 1H), 8.07 (d, J = 7.5 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.51 - 7.38 (m, 5H), 3.03 (s, 6H), confirming that the acenaphthene derivative B4 prepared has the structure shown in formula (3), wherein R1' is cyano, R2' is dimethylamine, R3', R4', R5', R6' are hydrogen, R' is phenyl.

[0210] Example B6

[0211] Into a reaction tube, 2 mL (25 eq) of N,N-dimethylformamide was added, after stirring and heating to 160 °C under nitrogen atmosphere, it was refluxed for 4 h, then 0.574 g (6.4 mmol, 16 eq) of cuprous cyanide and 216 mg (0.40 mmol, 1 eq) of acenaphthene derivative A5 were added, and the reaction was continued at 160 °C for 18 h. After the reaction was completed, it was cooled to room temperature, the solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by silica gel column chromatography with dichloromethane as eluent, and acenaphthene derivative B6 was obtained as a blue solid, weighing 0.046 g, with a calculated yield of 26%.

[0212] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 449.20 1 H NMR (400 MHz, Chloroform-d) δ 8.45 (d, J = 7.5 Hz, 1H), 8.36 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.27 (dd, J = 8.1, 6.7 Hz, 1H), 7.22 - 7.14 (m, 2H), 3.20 - 3.08 (m, 2H), 3.04 (s, 5H), 1.19 (d, J = 6.8 Hz, 12H), which proved that the acenaphthene derivative B6 prepared had a structure shown in formula (3), wherein R1' was cyano, R2' was dimethylamine, R3', R4', R5', R6' were hydrogen, and R' was 2,6-diisopropylphenyl.

[0213] Example B7

[0214] 0.172 g (1.92 mmol, 4.8 eq) of cuprous cyanide was weighed into a reaction tube, 2 mL (2.056 g) of N-methylpyrrolidone was added, and after stirring and heating to 160°C under a nitrogen atmosphere, 216 mg (0.40 mmol, 1 eq) of acenaphthene derivative A5 was added, and the reaction was continued at 160°C for 9 h. The solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by silica gel column chromatography with dichloromethane: petroleum ether = 1:1 as eluent, and acenaphthene derivative B7 was obtained as an orange yellow solid, weighing 0.042 g, with a calculated yield of 24%.

[0215] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 431.14 1 H NMR (400 MHz, Chloroform-d) δ 8.45 (d, J = 7.5 Hz, 1H), 8.36 (d, J = 7.5 Hz, 1H), 8.08 (d, J = 7.5 Hz, 1H), 8.02 (d, J = 7.5 Hz, 1H), 7.27 (dd, J = 8.1, 6.7 Hz, 1H), 7.22 - 7.14 (m, 2H), 3.20 - 3.08 (m, 2H), 3.04 (s, 5H), 1.19 (d, J = 6.8 Hz, 12H), which proved that the acenaphthene derivative B6 prepared had a structure shown in formula (3), wherein R1' was cyano, R2' was dimethylamine, R3', R4', R5', R6' were hydrogen, and R' was 2,6-diisopropylphenyl.

[0216] Example B8

[0217] To the reaction tube, 2 mL (25 eq) of N,N-dimethylformamide was added, and after stirring and heating to 160°C under a nitrogen atmosphere, 0.574 g (6.4 mmol, 16 eq) of cuprous cyanide and 152 mg (0.40 mmol, 1 eq) of acenaphthene derivative A6 were added, and the reaction was continued at 160°C for 18 hours. After the reaction was completed, the temperature was returned to room temperature, the solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by column chromatography on silica gel using dichloromethane as the eluent, and acenaphthene derivative B8 was obtained as a blue solid, 0.026 g, and the calculated yield was 22%.

[0218] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 289.07 1 H NMR (400 MHz, Chloroform-d) δ 8.34 (d, J = 7.5 Hz, 1H), 8.19 (d, J = 7.5 Hz, 1H), 8.05 (d, J = 7.5 Hz, 1H), 7.98 (d, J = 7.5 Hz, 1H), 3.04 (s, 6H), which proved that the acenaphthene derivative B8 prepared had the structure shown in formula (3), wherein R1' was a cyano group, R2' was a dimethylamine group, R3', R4', R5', R6' were hydrogen, and R' was a hydrogen atom.

[0219] Example B9

[0220] To the reaction tube, 0.172 g (1.92 mmol, 4.8 eq) of cuprous cyanide was added, 2 mL (2.056 g) of N-methylpyrrolidone was added, and after stirring and heating to 160°C under a nitrogen atmosphere, 152 mg (0.40 mmol, 1 eq) of acenaphthene derivative A6 was added, and the reaction was continued at 160°C for 9 hours. The solution was extracted with dichloromethane, and the organic phase was washed with brine. Purification was performed by column chromatography on silica gel using dichloromethane: petroleum ether = 1:1 as the eluent, and acenaphthene derivative B9 was obtained as an orange-yellow solid, 0.022 g, and the calculated yield was 20%.

[0221] The structure of the product was confirmed by nuclear magnetic hydrogen spectrum: MS (MALDI-TOF): 271.01 1 H NMR (400 MHz, Chloroform-d) δ 8.12 (d, J = 7.5 Hz, 2H), 8.00 (d, J = 7.5 Hz, 2H), which proved that the acenaphthene derivative B9 prepared had the structure shown in formula (3), wherein R1' and R2' were cyano groups, R3', R4', R5', R6' were hydrogen, and R' was a hydrogen atom.

[0222] Comparative Example 1

[0223] The compound shown in the following formula was prepared according to the method disclosed in the literature Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2021), 9(25), 7936-7949.

[0224]

[0225] Test Example

[0226] The acenaphthene derivative materials prepared in the above examples and comparative examples were used to prepare organic field effect transistor devices and test the performance of the devices.

[0227] A schematic diagram of a model of an organic field effect transistor device is shown in Figure 5 .

[0228] Silicon wafer cleaning: a silicon wafer with a silicon dioxide oxide layer (the thickness of the oxide layer is 300 nm, and the capacitance test is 11 nF / cm 2 ), before use, first clean with hydrogen peroxide and concentrated sulfuric acid (electric furnace heating, boiling) at a volume ratio of about 1:2, then sequentially clean with deionized water, anhydrous ethanol and acetone for about 10 minutes, and finally quickly dry with nitrogen. An octadecyltrichlorosilane (OTS) monolayer is prepared on the SiO2insulating layer by a vapor phase method as an insulating modification layer.

[0229] Device preparation: take the cleaned silicon wafer with the OTS modification on one side, deposit acenaphthene derivative material 30 μL on the silicon wafer at 185°C by a vapor phase method, after 6 hours, the deposited crystal is obtained, then an organic single crystal field effect device is prepared by the method of pasting a gold film (as the source and drain), and the test results are shown in Table 1.

[0230] The device performance of acenaphthene derivative material B1 was tested under a nitrogen atmosphere, and the transfer curve is shown in Figure 6 , the maximum single crystal electron mobility is measured to be 0.17 cm 2 V -1 s -1 , the on-off ratio is 10 4 -10 5 , and the threshold voltage is 5 to 15 V.

[0231] The device performance of acenaphthene derivative material B2 was tested under a nitrogen atmosphere, and the transfer curve is shown in Figure 7 , the maximum single crystal hole mobility is measured to be 3.9 x 10 -2 cm 2 V -1 s -1 , the on-off ratio is 10 4 -10 5The threshold voltage is -10 to -40 V.

[0232] The rest of the test example data is shown in Table 1.

[0233] Table 1

[0234]

[0235] It can be seen from the data in Table 1 that the acenaphthene derivative material prepared in the embodiment of the present application has good charge transport performance, and has an order of magnitude advantage in electrical performance compared with the material in the comparative example.

[0236] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A acenaphthene derivative, characterized in that, The acenaphthene derivative has the structure shown in formula (1). Equation (1), R1 and R2 are each independently selected from halogen atoms; R, R3, R4, R5, and R6 are each independently selected from hydrogen, halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, alkoxy groups, or alkylthio groups; The substituted or unsubstituted alkyl group is a C1-C15 alkyl group; the substituent in the substituted alkyl group is a halogen atom; The substituted or unsubstituted aryl group is a C6-C30 aryl group; the substituent in the substituted aryl group is a C1-C20 alkyl or halogen atom; The alkylthio group has 1-20 carbon atoms; The alkoxy group has 1-20 carbon atoms.

2. The acenaphthene derivative according to claim 1, wherein, The substituted or unsubstituted alkyl group is a straight-chain alkyl group or a branched alkyl group.

3. The acenaphthene derivative according to claim 1, wherein, R1 and R2 are each independently selected from chlorine, bromine, or iodine.

4. The acenaphthene derivative according to claim 3, wherein, R1 and R2 are each independently bromine.

5. The acenaphthene derivative according to claim 1, wherein, R is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, alkoxy or alkylthio, and R3, R4, R5, and R6 are hydrogen.

6. The acenaphthene derivative according to claim 5, wherein, R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-isopropylphenyl, p-isopropylphenyl, m-isopropylphenyl, 1-naphthyl, 2-naphthyl.

7. A method for preparing the acenaphthene derivative according to any one of claims 1-6, the method comprising: S1. The acenaphthene nucleus is subjected to a Friedel-Crafts acylation reaction; S2. The product obtained in step S1 is subjected to halogenation, anhydrideation and amidation reactions. The acenaphthene nucleus has the structure shown in formula (2). Equation (2).

8. The preparation method according to claim 7, wherein, Step S2 includes: S2-1. Contact the product obtained in step S1 with a halogenating reagent to carry out a halogenation reaction; S2-2, The product of the halogenation reaction is brought into contact with an acid to carry out anhydride reaction; S2-3. The product of the anhydride reaction is contacted with an amine compound to carry out an amidation reaction; The general formula of the amine compounds is R-NH2.

9. The preparation method according to claim 8, wherein, The halogenation reaction is a bromination reaction, and the conditions for the bromination reaction include: a reaction temperature of 70-100℃ and a reaction time of 1-10h.

10. The preparation method according to claim 8, wherein, The halogenating agent is selected from at least one of N-bromosuccinimide, liquid bromine, 1,3-dibromo-5,5-dimethylhydantoin, dibromoisocyanuric acid, and 1,3,5-tribromo-1,3,5-triazine-2,4,6-trione.

11. The preparation method according to claim 8, wherein, The amount of halogenating agent used is 1-10 equivalents relative to 1 equivalent of the product obtained in step S1.

12. The preparation method according to claim 8, wherein, The preparation method also includes introducing an oxidizing agent in step S2-1.

13. The preparation method according to claim 12, wherein, The oxidizing agent is at least one of benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, tert-butanol peroxide, and tert-butyl perbenzoate.

14. The preparation method according to claim 12, wherein, The amount of oxidizing agent used is 0.01-1 equivalent relative to 1 equivalent of the product obtained in step S1.

15. The preparation method according to claim 8, wherein, The halogenation reaction is carried out in the presence of the first solvent.

16. The preparation method according to claim 8, wherein, The conditions for the anhydride reaction include: a reaction temperature of 60-100℃ and a reaction time of 4-10h.

17. The preparation method according to claim 8, wherein, The acid is selected from inorganic acids and / or organic acids.

18. The preparation method according to claim 17, wherein, The acid is selected from at least one of hydrochloric acid, hydrobromic acid, sulfuric acid, and acetic acid.

19. The preparation method according to claim 8, wherein, The amount of acid used is 12-100 equivalents relative to the product of the halogenation reaction described in 1 equivalent.

20. The preparation method according to claim 18, wherein, The acid is provided by an aqueous solution of the acid, the concentration of which is 36-98 wt%.

21. The preparation method according to claim 8, wherein, The anhydride reaction was carried out under stirring conditions.

22. The preparation method according to claim 8, wherein, The conditions for the amidation reaction include: a reaction temperature of 80-150℃ and a reaction time of 36-60h.

23. The preparation method according to claim 8, wherein, The conditions for the amidation reaction include: first, a low-temperature reaction at 80-100℃ for 12-24 hours, and then a high-temperature reaction at 110-140℃ for 12-48 hours.

24. The preparation method according to claim 8, wherein, The amidation reaction was carried out under a protective atmosphere.

25. The preparation method according to claim 24, wherein, The protective atmosphere is provided by at least one of nitrogen, argon and neon.

26. The preparation method according to claim 8, wherein, The amidation reaction is carried out in the presence of a second solvent.

27. The preparation method according to claim 8, wherein, The amount of the amine compound used is 1-3 equivalents relative to 1 equivalent of the product of the anhydride reaction.

28. A acenaphthene-derived material, characterized in that, The acenaphthene-derived material is at least one of compounds having the structure shown in formula (3); Equation (3), Wherein, R1' and R2' are each independently a cyano or a C2-C10 dialkylamine group, and at least one of R1' and R2' is a cyano; R', R3', R4', R5', and R6' are each independently selected from hydrogen, halogen atoms, substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups, alkoxy groups, or alkylthio groups; The substituted or unsubstituted alkyl group is a C1-C15 alkyl group; the substituent in the substituted alkyl group is a halogen atom; The substituted or unsubstituted aryl group is a C6-C30 aryl group; the substituent in the substituted aryl group is a C1-C20 alkyl or halogen atom; The alkylthio group has 1-20 carbon atoms; The alkoxy group has 1-20 carbon atoms.

29. The acenaphthene-derived material according to claim 28, wherein, The substituted or unsubstituted alkyl group is a straight-chain alkyl group or a branched alkyl group.

30. The acenaphthene-derived material according to claim 28, wherein, R1' and R2' are each independently either cyano or dimethylamino, and at least one of R1' and R2' is cyano.

31. The acenaphthene-derived material according to claim 28, wherein, R' is selected from substituted or unsubstituted alkyl, substituted or unsubstituted aryl, alkoxy or alkylthio; R3', R4', R5', and R6' are hydrogen.

32. The acenaphthene-derived material according to claim 31, wherein, R' represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, n-hexyl, n-heptyl, n-octyl, isooctyl, n-nonyl, phenyl, fluorophenyl, bromophenyl, chlorophenyl, o-tolyl, p-tolyl, m-tolyl, o-ethylphenyl, p-ethylphenyl, m-ethylphenyl, o-isopropylphenyl, p-isopropylphenyl, m-isopropylphenyl, 1-naphthyl, 2-naphthyl.

33. A method for preparing an acenaphthene-derived material, the method comprising: The acenaphthene derivative, cyaniding agent, and third solvent described in any one of claims 1-6 are mixed, and then a cyanidation reaction is carried out. The amount of the cyaniding agent used is 4-10 equivalents relative to 1 equivalent of the acenaphthene derivative.

34. The preparation method according to claim 33, wherein, The cyaniding agent is selected from at least one of cuprous cyanide, zinc cyanide, and potassium ferrocyanide; The third solvent is selected from at least one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, and N,N-dimethylbutyramide.

35. The preparation method according to claim 33, wherein, The conditions for the cyanidation reaction include: a temperature of 100-200℃ and a time of 8-48h.

36. The preparation method according to claim 33, wherein, The cyanidation reaction is carried out under a protective atmosphere.

37. The preparation method according to claim 36, wherein, The protective atmosphere is provided by at least one of nitrogen, argon and neon.

38. The preparation method according to claim 33, wherein, The cyanidation reaction was carried out under stirring conditions.

39. Acenaparin-derived materials prepared by the preparation method according to any one of claims 33-38.

40. A method for preparing an acenaphthene-derived material, the method comprising: Step B1: Heating and refluxing the dialkylamine raw material; the dialkylamine raw material is selected from at least one of N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethylpropionamide, N,N-dimethylbutyramide, N-ethylformamide, N,N-diethylformamide, N,N-dipropylformamide, N,N-dibutylformamide, and N,N-dipentylformamide. Step B2: Contact the product obtained in step B1, the acenaphthene derivative according to any one of claims 1-6, with a cyaniding reagent to carry out the reaction.

41. The preparation method according to claim 40, wherein, The cyaniding agent is selected from at least one of cuprous cyanide, zinc cyanide, and potassium ferrocyanide.

42. The preparation method according to claim 40, wherein, The amount of the cyaniding agent used is 4-30 equivalents relative to 1 equivalent of the acenaphthene derivative.

43. The preparation method according to claim 40, wherein, The amount of the dialkylamine raw material used is 20-40 equivalents relative to 1 equivalent of the acenaphthene derivative.

44. The preparation method according to claim 40, wherein, In step B1, the heating temperature is 100-200℃.

45. The preparation method according to claim 40, wherein, The reflux time is 1-4 hours.

46. ​​The preparation method according to claim 40, wherein, In step B2, the reaction conditions include: a temperature of 100-200℃ and a time of 12-48h.

47. The preparation method according to claim 40, wherein, The reaction was carried out under a protective atmosphere.

48. The preparation method according to claim 47, wherein, The protective atmosphere is provided by at least one of nitrogen, argon and neon.

49. The preparation method according to claim 40, wherein, The reaction was carried out under stirring conditions.

50. Acenamel-derived materials prepared by the preparation method according to any one of claims 40-49.

51. The use of the acenaphthene-derived material according to any one of claims 28-32, 39 or 50 in a field-effect transistor.

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