Fluorene derivative as well as preparation method and application thereof

Abstract

Disclosed are a compound of formula (I) wherein two R are the same or different, two R1 are the same or different, and each R and R1 are independently selected from the group consisting of the following unsubstituted or optionally substituted by one, two, three or more Ra: C1-40 alkyl, C2-40 alkenyl, C2-40 alkynyl, C1-40 alkoxy, C1-40 alkylthio, C6-30 aryl, 5-30 membered heteroaryl, or-NRbRc. The compound of the formula (I) can be used as an organic semiconductor material, a material with an amplified self-emission phenomenon and an organic solid laser material, and can be applied to an organic field effect transistor and / or an organic solid laser and / or an organic light-emitting field effect transistor. # imgabs0 #

Description

Technical Field

[0001] The invention belongs to the fields of organic optoelectronics, organic solid laser and chemical synthesis, and specifically relates to fluorene derivatives and preparation methods and applications thereof. Background Art

[0002] In the 1970s, the discovery of conductive polymers opened the door to a new field of organic electronics research. Organic semiconductor materials with π structures attracted the attention of scientists. They have been widely used in organic field effect transistors, organic light-emitting diodes, organic solar cells, organic solid-state lasers and organic light-emitting field effect transistors. However, to date, the realization of organic electrically pumped lasers still faces huge challenges, which also puts forward new requirements for organic semiconductor materials. Organic semiconductors must not only have high fluorescence quantum yields and good charge transfer capabilities, but also have good optical gain to ensure their good laser performance. The design and synthesis of this type of organic semiconductor material has brought new challenges to scientists, and the discovery of fluorene derivatives has brought us new opportunities. Fluorene is a polycyclic aromatic hydrocarbon composed of two benzene rings and a five-membered ring in the middle. The molecular formula is C 13 H 10 , white flaky crystals, fluorene itself has purple fluorescence and a characteristic aromatic smell similar to naphthalene. It mainly exists in high-boiling point components of automobile exhaust, corn silk, and coal tar. Through literature research, it is found that fluorene derivatives have good luminescence and laser properties. The inventor hopes to further improve its electrical properties by expanding the conjugated system, and develop a type of organic semiconductor material with excellent electrical properties, luminescence properties and laser properties, laying a material foundation for the research of high-performance organic transistor devices, organic light-emitting diode devices, organic light-emitting field-effect transistor devices, organic electrically pumped lasers and related organic optoelectronic functional devices.

[0003] In 1989, Yoshino and his collaborators modified the 9-position of fluorene with an alkyl chain by oxidative coupling and synthesized soluble polyalkylfluorene. In 1996, Pei and Yang synthesized a conjugated polyfluorene derivative with a high molecular weight by metal catalysis. The film of the polymer has a strong blue fluorescence with a fluorescence quantum yield (PLQY) of 73%. In 2006, Professor Sirringhaus's team used gold as an electrode and polymethyl methacrylate (PMMA) as an insulating layer to construct an organic light-emitting field-effect transistor (OLET) device with a top-gate bottom contact based on poly (9,9-dioctylfluorene-co-benzothiadiazole) (F8BT), with a mobility of 0.01 cm 2 V -1 s -1, reflecting good charge transfer performance. At present, fluorene derivatives with good photoelectric properties are constantly being designed and synthesized, showing important applications in organic optoelectronic devices. Therefore, the superior photoelectric properties of organic semiconductor materials with fluorene as the core make the research in this field not only of theoretical value, but also in the research of new organic optoelectronic devices, such as organic field effect transistors, organic electroluminescent devices, organic light-emitting field effect transistors, organic electrically pumped lasers and related optoelectronic functional devices. It has potential application prospects. Summary of the invention

[0004] The present invention provides a compound having a structure shown in the following formula (I):

[0005]

[0006] wherein two R are the same or different, two R1 are the same or different, and each R and R1 are independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted with the following groups: C 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl, C 1-40 Alkoxy, C 1-40 Alkylthio, C 6-30 Aryl, 5-30 membered heteroaryl or -NR b R c ;

[0007] Among them, each R a are independently selected from nitro, cyano, hydroxy, halogen, unsubstituted or optionally substituted with one, two, three or more halogen, hydroxy, cyano or nitro. 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl, C 1-40 Alkoxy, C 1-40 Alkylthio, C 6-30 Aryl, 5-30 membered heteroaryl or -NR b R c ;

[0008] The R b and R c are the same or different and are independently selected from hydrogen, unsubstituted or optionally substituted by one, two, three or more halogen, hydroxyl, cyano or nitro 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl, C 6-30 aryl or 5-30 membered heteroaryl, provided that R b and R cNot at the same time hydrogen;

[0009] Preferably, the two R1 are independently selected from hydrogen, unsubstituted or C optionally substituted by one, two, three or more halogen, hydroxyl, cyano or nitro. 1-40 Alkyl, C 2-40 Alkenyl, C 2-40 Alkynyl, C 1-40 Alkoxy, C 1-40 Alkylthio, C 6-30 Aryl, 5-30 membered heteroaryl.

[0010] According to an embodiment of the present invention, in the compound of formula (I),

[0011] Two R are the same or different, two R1 are the same or different, each R and R1 are independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted with the following groups: C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 1-10 Alkoxy, C 1-10 Alkylthio, C 6-14 Aryl, 5-14 membered heteroaryl or -NR b R c ;

[0012] Among them, each R a are independently selected from nitro, cyano, hydroxy, halogen, unsubstituted or optionally substituted with one, two, three or more halogen, hydroxy, cyano or nitro. 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 1-10 Alkoxy, C 1-10 Alkylthio, C 6-14 Aryl, 5-14 membered heteroaryl or -NR b R c ;

[0013] The R b and R c are the same or different and are independently selected from hydrogen, unsubstituted or optionally substituted by one, two, three or more halogen, hydroxyl, cyano or nitro 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-14 aryl or 5-14 membered heteroaryl, provided that R b and R c Not at the same time hydrogen;

[0014] Preferably, the two R1 are independently selected from hydrogen, unsubstituted or C optionally substituted by one, two, three or more halogen, hydroxyl, cyano or nitro. 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 1-10 Alkoxy, C 1-10 Alkylthio, C 6-14 Aryl, 5-14 membered heteroaryl.

[0015] According to an embodiment of the present invention, in the compound of formula (I),

[0016] Two R are the same or different, two R1 are the same or different, each R and R1 are independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted C 6-14 Aryl or 5-14 membered heteroaryl;

[0017] Among them, each R a are independently selected from nitro, cyano, hydroxy, halogen, unsubstituted or optionally substituted with one, two, three or more halogen, hydroxy, cyano or nitro. 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 6-14 Aryl, 5-14 membered heteroaryl or -NR b R c ;

[0018] The R b and R c are the same or different and are independently selected from C which is unsubstituted or optionally substituted with one, two, three or more halogen, hydroxyl, cyano or nitro 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 6-14 Aryl or 5-14 membered heteroaryl;

[0019] Preferably, the two R1 are independently selected from hydrogen, unsubstituted or C optionally substituted by one, two, three or more halogen, hydroxyl, cyano or nitro. 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 1-6 Alkoxy, C 1-6 Alkylthio, C 6-14 Aryl, 5-14 membered heteroaryl.

[0020] According to an embodiment of the present invention, in the compound of formula (I),

[0021] Two R are the same or different, two R1 are the same or different, each R and R1 are independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted C 6-14 Aryl or 5-14 membered heteroaryl;

[0022] Among them, each R a are independently selected from nitro, cyano, hydroxy, halogen, methyl, trifluoromethyl, ethyl, propyl, butyl, phenyl, halophenyl, cyanophenyl, hydroxyphenyl, pyranyl, halopyranyl, cyanopyranyl, hydroxypyranyl, thienyl, halopyranyl, cyanothiphenyl, hydroxythienyl, thiazolyl, halothiazolyl, cyanothiazolyl, hydroxythiazolyl, thiadiazolyl, halopyranyl, cyanothiazolyl, hydroxythiadiazolyl or diphenylamino;

[0023] Preferably, the two R1 are independently selected from hydrogen, methyl, trifluoromethyl, ethyl, propyl, butyl, phenyl, and halophenyl.

[0024] According to an embodiment of the present invention, in the compound of formula (I),

[0025] Two R are the same or different, two R1 are the same or different, each R and R1 are independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted phenyl, naphthyl, thienyl, furanyl, anthracenyl, pyridyl, pyrimidinyl, pyrazinyl, thiazolyl, thiadiazolyl, phenazinyl, quinolyl, quinazolinyl or thienyl;

[0026] Among them, each R a are independently selected from nitro, cyano, hydroxy, halogen, methyl, trifluoromethyl, ethyl, propyl, butyl, phenyl, halophenyl, cyanophenyl, hydroxyphenyl, pyranyl, halopyranyl, cyanopyranyl, hydroxypyranyl, thienyl, halopyranyl, cyanothiphenyl, hydroxythienyl, thiazolyl, halothiazolyl, cyanothiazolyl, hydroxythiazolyl, thiadiazolyl, halopyranyl, cyanothiazolyl, hydroxythiadiazolyl or diphenylamino;

[0027] Preferably, two R1 are independently selected from hydrogen, methyl, ethyl, propyl, butyl.

[0028] According to an embodiment of the present invention, in the compound of formula (I),

[0029] Two R's are the same or different, two R's are the same or different, and each R and R' is independently selected from the following groups: phenyl, naphthyl, thienyl, furanyl, trifluorophenyl, anthracenyl, pyridyl, pyrazinyl, thiazolyl, thiadiazolyl, phenazinyl, quinolyl, quinazolinyl, trifluoromethylphenyl, cyanophenyl, thienylphenyl, dithienyl, trithienyl, tetrathienyl, (diphenylamino)phenyl, trifluorothienylphenyl, phenylthienyl 4-n-butyl-phenyl, 2-(2-ethylhexyl)-1H benzisoquinoline-1,3(2H)-dione, trinitrophenyl;

[0030] Preferably, the two R1 are independently selected from hydrogen or methyl.

[0031] According to an embodiment of the present invention, the compound of formula (I) is selected from the following compounds:

[0032]

[0033]

[0034] The present invention also provides a method for preparing the compound of formula (I), which can be one of the following methods:

[0035] Method (a): Compound A is reacted with compound RB(OR')2 to obtain a compound of formula (I):

[0036]

[0037] wherein R and R1 have the above definitions, X is a halogen, such as fluorine, chlorine, bromine or iodine; two R's are the same or different and are independently selected from hydrogen, C 1-6 Alkyl, C 1-6 Alkenyl, C 1-6 Alkynyl, C 6-14 Aryl or 5-14 membered heteroaryl, or two R together with the O atom to which they are attached and the B atom form a 5-10 membered ring;

[0038] Method (b): comprising the following steps:

[0039] Step (1): Compound A is reacted with compound bis(pinacol)diboron to obtain compound C-1:

[0040]

[0041] and

[0042] Step (2): reacting compound C-1 with compound RX to obtain a compound of formula (I):

[0043]

[0044] wherein R and R1 have the definitions given above, and X is a halogen, such as fluorine, chlorine, bromine or iodine;

[0045] or,

[0046] Method (c): Compound C-2 is reacted with compound RX to obtain a compound of formula (I):

[0047]

[0048] wherein R and R1 have the above-mentioned meanings and X is a halogen such as fluorine, chlorine, bromine or iodine.

[0049] According to an embodiment of the present invention, the reaction of the above method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) can be carried out in the presence of a base, which can be one, two or more of sodium carbonate, cesium carbonate or potassium carbonate.

[0050] According to an embodiment of the present invention, the reaction of the above method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) can be carried out in the presence of a catalyst, and the catalyst can be a palladium catalyst, for example, one, two or more of tetrakistriphenylphosphine palladium, 1,1'-bis(diphenylphosphinodiphenylferrocene)palladium dichloride or palladium acetate.

[0051] According to an embodiment of the present invention, in the above method (a), the compound RB(OR')2 can be One of the above, wherein R has the definition described above; for example, the compound RB(OR')2 can be phenylboronic acid, 2-naphthaleneboronic acid or 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline; R1 has the definition described above; for example, hydrogen, methyl.

[0052] According to an embodiment of the present invention, the reaction time of the above method (a), the reaction of steps (1) and (2) of method (b) and the reaction time of method (c) can be 5-72 hours, for example, 6-48 hours, such as 10-24 hours.

[0053] According to an embodiment of the present invention, the reaction temperature of the above method (a), the reaction of steps (1) and (2) of method (b) and the reaction of method (c) can be 80-180°C, for example, 90-150°C, such as 100-120°C.

[0054] According to an embodiment of the present invention, the reaction of the above method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) can be carried out in an organic solvent, and the solvent can be one, two or more of methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, dimethylformamide, toluene or dioxane.

[0055] According to an embodiment of the present invention, the reaction of the above method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) can be carried out under the protection of an inert gas, wherein the inert gas is a gas inert to the reaction, such as nitrogen or argon.

[0056] The present invention provides the use of the compound of formula (I) as an organic semiconductor material in an organic optoelectronic device, preferably in the preparation of an organic field effect transistor (OFET), an organic light-emitting field effect transistor (OLET), an organic photo-controlled transistor, an organic light-emitting diode and related functional devices, as well as in amplifying spontaneous emission phenomena, an organic solid-state laser and related functional devices.

[0057] According to an embodiment of the present invention, the organic semiconductor material is a thin film and / or crystal of multiple crystal phases obtained by a physical vapor deposition method.

[0058] The present invention also provides an organic field effect transistor, which comprises the compound of formula (I).

[0059] According to an embodiment of the present invention, the semiconductor layer of the organic field effect transistor includes the compound of formula (I).

[0060] According to an embodiment of the present invention, the semiconductor layer is an organic thin film layer and / or an organic single crystal layer.

[0061] According to an embodiment of the present invention, the organic field effect transistor includes an organic thin film field effect transistor and / or an organic single crystal field effect transistor.

[0062] According to an embodiment of the present invention, the organic field effect transistor includes a P-type organic field effect transistor, an N-type organic field effect transistor and / or a bipolar organic field effect transistor.

[0063] According to an embodiment of the present invention, the compound of formula (I) has amplified spontaneous emission properties.

[0064] According to an embodiment of the present invention, an organic thin film layer, an organic single crystal layer and / or a solution containing a compound of formula (I) has amplified spontaneous emission properties.

[0065] The present invention also provides an organic solid laser, wherein the organic solid laser comprises the compound of formula (I).

[0066] According to an embodiment of the present invention, the gain medium of the organic solid laser comprises a compound of formula (I).

[0067] According to an embodiment of the present invention, the gain medium is an organic thin film layer, an organic single crystal layer and / or a solution.

[0068] According to an embodiment of the present invention, the organic solid laser may generate laser light in a solution, a thin film, or an organic single crystal.

[0069] According to an embodiment of the present invention, the organic solid laser includes an organic thin film laser and / or an organic single crystal laser and / or an organic solution laser.

[0070] The present invention also provides a horizontal organic light-emitting field effect transistor, which comprises a compound of formula (I).

[0071] According to an embodiment of the present invention, the semiconductor layer of the horizontal organic light emitting field effect transistor includes a compound of formula (I).

[0072] According to an embodiment of the present invention, the semiconductor layer is an organic thin film layer and / or an organic single crystal layer.

[0073] According to an embodiment of the present invention, the horizontal organic light emitting field effect transistor includes a horizontal organic thin film light emitting field effect transistor and / or a horizontal organic single crystal light emitting field effect transistor.

[0074] The present invention also provides a vertical organic light-emitting field effect transistor, which comprises a compound of formula (I).

[0075] According to an embodiment of the present invention, the semiconductor layer of the vertical organic light emitting field effect transistor includes a compound of formula (I).

[0076] According to an embodiment of the present invention, the semiconductor layer is an organic thin film layer and / or an organic single crystal layer.

[0077] According to an embodiment of the present invention, the vertical organic light emitting field effect transistor includes a vertical organic thin film light emitting field effect transistor and / or a vertical organic single crystal light emitting field effect transistor.

[0078] Terminology and Explanation

[0079] Unless otherwise defined, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.

[0080] The term "C 1-40"Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 40 carbon atoms. For example, "C 1-10 "Alkyl" means straight chain and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 1-6 The term "alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5 or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl or 1,2-dimethylbutyl, or the like or isomers thereof.

[0081] The term "C 2-40 "Alkenyl" is understood to mean preferably a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2 to 40 carbon atoms, preferably "C 2-10 "C 2-10 The term "alkenyl" is understood to mean preferably a linear or branched monovalent hydrocarbon radical containing one or more double bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, for example having 2, 3, 4, 5 or 6 carbon atoms (i.e., C 2-6 alkenyl), having 2 or 3 carbon atoms (i.e., C 2-3It is understood that where the alkenyl group contains more than one double bond, the double bonds may be separated from one another or conjugated. The alkenyl group is, for example, vinyl, allyl, (E)-2-methylvinyl, (Z)-2-methylvinyl, (E)-but-2-enyl, (Z)-but-2-enyl, (E)-but-1-enyl, (Z)-but-1-enyl, pent-4-enyl, (E)-pent-3-enyl, (Z)-pent-3-enyl, (E)-pent-2-enyl, (Z)-pent-2-enyl, (E)- Pent-1-enyl, (Z)-pent-1-enyl, hex-5-enyl, (E)-hex-4-enyl, (Z)-hex-4-enyl, (E)-hex-3-enyl, (Z)-hex-3-enyl, (E)-hex-2-enyl, (Z)-hex-2-enyl, (E)-hex-1-enyl, (Z)-hex-1-enyl, isopropenyl, 2-methylprop-2-enyl, 1-methylprop-2-enyl , 2-methylprop-1-enyl, (E)-1-methylprop-1-enyl, (Z)-1-methylprop-1-enyl, 3-methylbut-3-enyl, 2-methylbut-3-enyl, 1-methylbut-3-enyl, 3-methylbut-2-enyl, (E)-2-methylbut-2-enyl, (Z)-2-methylbut-2-enyl, (E)-1-methylbut-2-enyl, (Z)-1-methyl but-2-enyl, (E)-3-methylbut-1-enyl, (Z)-3-methylbut-1-enyl, (E)-2-methylbut-1-enyl, (Z)-2-methylbut-1-enyl, (E)-1-methylbut-1-enyl, (Z)-1-methylbut-1-enyl, 1,1-dimethylprop-2-enyl, 1-ethylprop-1-enyl, 1-propylvinyl, 1-isopropylvinyl.

[0082] The term "C 2-40 "Alkynyl" is understood to mean a linear or branched monovalent hydrocarbon radical containing one or more triple bonds and having 2 to 40 carbon atoms, preferably "C 2-10 The term "C 2-10 "Alkynyl" is understood to mean preferably a straight or branched monovalent hydrocarbon radical containing one or more triple bonds and having 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, for example having 2, 3, 4, 5 or 6 carbon atoms (i.e., "C 2-6 Alkynyl”), having 2 or 3 carbon atoms (“C 2-3The alkynyl group is, for example, ethynyl, prop-1-ynyl, prop-2-ynyl, but-1-ynyl, but-2-ynyl, but-3-ynyl, pent-1-ynyl, pent-2-ynyl, pent-3-ynyl, pent-4-ynyl, hex-1-ynyl, hex-2-ynyl, hex-3-ynyl, hex-4-ynyl, hex-5-ynyl, 1-methylprop-2-ynyl, 2-methylbut-3-ynyl, 1-methylbut-3-ynyl, 1-methylbut-2-ynyl, 3-methylbut-1-ynyl, 1-ethylprop-2-ynyl, 3-methylpent-4-ynyl, 2-methylpent-4-ynyl, 1-methylpent-4 In some embodiments, the alkynyl group is ethynyl, prop-1-ynyl or prop-2-ynyl.

[0083] The term "C 1-40 "Alkoxy" is understood to mean -OC 1-40 Alkyl, where C 1-40 Alkyl has the above definition.

[0084] The term "C 1-40 "Alkylthio" is understood to mean -SC 1-40 Alkyl, where C 1-40 Alkyl has the above definition.

[0085] The term "C 6-30 "Aryl" is understood to mean a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 30 carbon atoms, preferably 6 to 14 carbon atoms. 6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 or a ring having 9 carbon atoms ("C9 aryl"), for example indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C6-14 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0086] The term "heteroaryl" is to be understood as a monovalent monocyclic, bicyclic or tricyclic aromatic ring radical having 5 to 30 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, for example "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is to be understood as a monovalent monocyclic, bicyclic or tricyclic aromatic ring radical having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which contains 1 to 5, preferably 1 to 3, heteroatoms independently selected from N, O and S, and, in each case, may additionally be benzo-fused. In particular, the heteroaryl group is selected from thienyl, furanyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl and the like and benzo derivatives thereof, such as benzofuranyl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl and the like.

[0087] The term "halogen" refers to fluorine, chlorine, bromine or iodine.

[0088] Beneficial effects of the present invention:

[0089] 1. The compound of formula (I) of the present invention can be controllably prepared into compounds of multiple crystal phases (thin films and / or single crystals) of the compound of formula (I) by physical vapor deposition, and each crystal phase has good photoelectric properties.

[0090] 2. The compound of formula (I) of the present invention can be used as an active layer of an organic semiconductor in a photoelectric device:

[0091] 2.1 The maximum hole mobility of the single-crystal field effect transistor prepared by using the compound of formula (I) of the present invention as an organic semiconductor layer is up to 0.7 cm 2 V -1 s -1 ,The preparation and testing of organic field-effect transistors are relatively simple and are all completed under atmospheric conditions;

[0092] 2.2 The horizontal organic light-emitting field effect transistor prepared by using the compound of formula (I) of the present invention as an organic semiconductor layer shows good light-emitting properties. The device preparation and testing of the horizontal organic light-emitting field effect transistor are completed in a glove box;

[0093] 2.3 The vertical organic light-emitting field effect transistor prepared by using the compound of formula (I) of the present invention as an organic semiconductor layer showed good light-emitting characteristics. The device preparation and testing of the vertical organic light-emitting field effect transistor were completed in a glove box.

[0094] 3. The compound of formula (I) of the present invention has the property of amplified spontaneous emission, and has the characteristics of low threshold, high gain, low loss, etc.

[0095] 4. The compound of formula (I) of the present invention can be used as a material for an organic solid laser, and the material has the characteristics of a low threshold and a high quality factor.

[0096] 5. The compound of formula (I) of the present invention has both high charge transport capability and good solid-state laser characteristics, and is a good class of organic optoelectronic functional materials, providing a material basis for the realization of organic electrically pumped lasers.

[0097] 6. The preparation method of the compound of formula (I) of the present invention has the advantages of simple reaction route, high efficiency, environmental friendliness, low raw material price and low synthesis cost; the preparation method has the characteristics of high universality and good repeatability. BRIEF DESCRIPTION OF THE DRAWINGS

[0098] Figure 1 The UV-visible absorption spectrum (a), cyclic voltammetry curve (b) and thermal decomposition temperature curve (c) of the solution of 2,7-diphenylfluorene (LD-1) in dichloromethane of Example 1 are shown.

[0099] Figure 2 The UV-visible absorption spectrum (a) and cyclic voltammetry curve (b) of the solution of 2,7-dinaphthylfluorene (LD-2) in chloroform of Example 2 are shown.

[0100] Figure 3 The UV-visible absorption spectrum (a) and cyclic voltammetry curve (b) of the solution of 2,7-dithienylfluorene (LD-3) in chloroform of Example 3 are shown.

[0101] Figure 4 The UV-visible absorption spectrum (a) and cyclic voltammetry curve (b) of 2,7-diquinolinylfluorene (LD-4) of Example 4 in chloroform solution are shown.

[0102] Figure 5 The single crystal data structure of the α-phase 2,7-diphenylfluorene (LD-1) of Example 1 is shown.

[0103] Figure 6 The single crystal data structure of the β-phase 2,7-diphenylfluorene (LD-1) of Example 1 is shown.

[0104] Figure 7 The schematic diagram of the structure of the organic field effect transistor prepared in Example 6 is shown.

[0105] Figure 8 The transfer curve and output curve of the α-phase 2,7-diphenylfluorene (LD-1) single crystal field effect transistor device of Example 1 are shown.

[0106] Fig. 9 The transfer curve of the β-phase 2,7-diphenylfluorene (LD-1) single crystal field effect transistor device of Example 1 is shown.

[0107] Fig.10 The transfer curve and output curve of the 2,7-dinaphthylfluorene (LD-2) single crystal field effect transistor device of Example 2 are shown.

[0108] Fig.11 The transfer curve of the 2,7-dithienylfluorene (LD-3) single crystal field effect transistor device of Example 3 is shown.

[0109] Fig.12 The amplified spontaneous emission properties and threshold curve of 2,7-diphenylfluorene (LD-1) tested in Example 7 are shown.

[0110] Fig.13 The spectrum of 2,7-diphenylfluorene (LD-1) tested in Example 8 in an organic solid laser is shown.

[0111] Fig.14 A microscope photograph of the horizontal organic light-emitting field-effect transistor prepared in Example 9 is shown.

[0112] Fig.15 The electroluminescence spectrum of the horizontal organic light-emitting field-effect transistor prepared in Example 9 is shown.

[0113] Fig.16 A microscope photograph of the vertical organic light-emitting field-effect transistor prepared in Example 10 is shown.

[0114] Fig.17 The current density curve and electroluminescence spectrum of the vertical organic light-emitting field-effect transistor prepared in Example 10 are shown. DETAILED DESCRIPTION

[0115] The present invention will be further described below in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present invention and are not intended to limit the scope of protection of the present invention. In addition, it should be understood that after reading the contents disclosed in the present invention, those skilled in the art may make various changes or modifications to the present invention, and these equivalent forms also fall within the scope of protection defined by the present invention.

[0116] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods; the reagents, materials, etc. used in the following examples, unless otherwise specified, can be obtained from commercial channels.

[0117] Example 1: Preparation of 2,7-diphenylfluorene (LD-1)

[0118]

[0119] Add reactants 2,7-dibromofluorene (1g, 3mmol), phenylboronic acid (1.463g, 12mmol) and tetrakistriphenylphosphine palladium (208mg, 0.06eq.) to a dry two-necked flask. Then, replace the inert gas through a vacuum oil pump-double-row tube, slowly add 30mL of toluene and 6mL of potassium carbonate solution to the flask with a syringe, and heat the whole system to 100℃ and stir for 72 hours under an argon atmosphere. After the reaction is completed and cooled to room temperature, add 75mL of chloroform solution to extract three times, add desiccant magnesium sulfate to the organic phase for drying, remove the organic solvent by vacuum distillation, and pass through a silica gel column (petroleum ether: dichloromethane = 10:1) to obtain a white powder (LD-1) with a mass of 0.6g and a yield of 61%.

[0120] The structural confirmation data of the product are as follows:

[0121] Mass spectrum: MS (EI): m / z: 318 (M + ).

[0122] H NMR spectrum: 1 H NMR (CDCl3): δ = 4.03 (s, 2H), 7.36 (t, J = 7.36Hz, 2H), 7.47 (t, J = 7.36Hz, 4H), 7.66 (t, J = 8.46Hz, 6H), 7.8 (s, 2H), 7.87 (d, J = 7.86Hz, 2H).

[0123] Calculated value C from elemental analysis 25 H 28 (%): C: 94.30, H: 5.70. Measured value: C: 93.96%, H: 5.69%.

[0124] The spectral properties, electrochemical properties and thermodynamic properties of the obtained white solid product were determined as follows:

[0125] (1) Spectral properties of LD-1

[0126] Figure 1 (a) is the UV-visible absorption spectrum of LD-1 in dichloromethane solution. As can be seen from the figure, the maximum absorption peak of LD-1 in dichloromethane solution is 324nm.

[0127] (2) Electrochemical properties of LD-1

[0128] The three-electrode system was used for testing: the working electrode was a glassy carbon electrode, the platinum wire was the counter electrode, the Ag / AgCl was the reference electrode, and Bu4NPF6 was the supporting electrolyte. The test conditions were: the scanning range was 0-2.0V (vs.Ag / AgCl), and the scanning rate was 100mV / s. Figure 1 (b) is the cyclic voltammetry curve of LD-1. The electrochemical test results show that the initial oxidation potential of LD-1 is 1.35 eV, and the highest occupied orbital energy level (HOMO) energy level calculated from it is -5.76 eV, indicating that LD-1 has high oxidation stability.

[0129] (3) Thermodynamic properties of LD-1

[0130] Figure 1 (c) is the thermal gravimetric analysis (TGA) curve of LD-1. From the curve analysis, it can be seen that compound LD-1 shows excellent thermal stability, and its thermal decomposition temperature is 337°C.

[0131] Example 2: Preparation of 2,7-dinaphthylfluorene (LD-2)

[0132]

[0133] In a dry two-necked flask, add the reactants 2,7-dibromofluorene (1g, 3mmol), 2-naphthoboric acid (2g, 11.6mmol), palladium acetate (27mg), tri-tert-butylphosphine tetrafluoroborate (41mg), and potassium fluoride (1.4g, 24mmol). Then, through the vacuum oil pump-double-row tube, argon gas is replaced, and 1,4-dioxane 15mL is slowly added to the flask in sequence with a syringe. The whole system is heated to 100℃ and stirred for 24 hours under an argon atmosphere. After the reaction is completed and cooled to room temperature, extraction is performed, magnesium sulfate is added to the organic phase for drying, and the organic solvent is removed by vacuum distillation. After passing through a silica gel column (petroleum ether: dichloromethane = 5:1), a white powder 2,7-dinaphthylfluorene (LD-2) is obtained, with a mass of 1.228g and a yield of 95%.

[0134] The structural confirmation data of the product are as follows:

[0135] Mass Spectrometry: EI:M+ :418.

[0136] Mass spectrometry: MS (MALDI-TOF): calculated value M - ,418; measured value,418.

[0137] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ (ppm): 8.13 (s, 2H), 7.94 (m, 8H), 7.88 (d, 2H), 7.84 (d, 2H), 7.79 (d, 2H), 7.5 (m, 4H), 4.1 (s, 2H).

[0138] The spectral properties, electrochemical properties and thermodynamic properties of the obtained white solid product were determined as follows:

[0139] (1) Spectral properties of LD-2

[0140] Figure 2 (a) is the UV-visible absorption spectrum of 2,7-dinaphthylfluorene in chloroform solution. As can be seen from the figure, the maximum absorption peak of LD-2 in chloroform solution is 334nm.

[0141] (2) Electrochemical properties of LD-2

[0142] The three-electrode system was used for testing: the working electrode was a glassy carbon electrode, the platinum wire was the counter electrode, the Ag / AgCl was the reference electrode, and Bu4NPF6 was the supporting electrolyte. The test conditions were: the scanning range was 0-1.6V (vs.Ag / AgCl), and the scanning rate was 100mV / s. Figure 2 (b) is the cyclic voltammetry curve of 2,7-dinaphthylfluorene (LD-2) in chloroform solution. Electrochemical tests show that the initial oxidation potential of LD-2 is 1.14V, and the highest occupied orbital energy level (HOMO) energy level calculated from this is -5.54eV.

[0143] Example 3: Preparation of 2,7-dithienylfluorene (LD-3)

[0144]

[0145] Add the substrate 2,7-dibromofluorene (2g, 6mmol), bis-pinacol diboron (7.6g, 30mmol), potassium acetate (2.352g, 24mmol) 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (0.246g, 0.3mmol) into a dry two-necked flask. Then add 30mL of dimethyl sulfoxide and bubble for 15 minutes under a nitrogen atmosphere to exclude air. The reaction was maintained at 100°C and stirred for 24 hours under a nitrogen atmosphere. When the reaction was completed and cooled to room temperature, dichloromethane was extracted and the organic layer was dried with a desiccant magnesium sulfate. The solvent was removed by vacuum distillation and passed through a silica gel column with petroleum ether / dichloromethane (10:1). The polarity was gradually increased from 5:1 to 2:1, and finally the product 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluorene was obtained with a mass of 2.5 g and a yield of 96.9%.

[0146] The structural confirmation data of the product are as follows:

[0147] Mass Spectrometry: EI:M + :418.

[0148] Mass spectrometry: MS (MALDI-TOF): calculated value M - ,418; measured value,418.

[0149] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ (ppm): 8.01 (s, 2H), 7.83 (s, 4H), 3.89 (s, 2H), 1.37 (m, 24H).

[0150]

[0151] 2-Bromothiophene (0.86 g, 5.28 mmol), 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-fluorene (1.0 g, 2.4 mmol), catalyst tetrakistriphenylphosphine palladium (55 mg, 0.02 eq.), trioctylmethylammonium chloride (0.48 g, 1.2 mmol) were added to a dry two-necked flask, and argon was passed through the flask under vacuum. Sodium carbonate (1.3 g, 12 mmol) was dissolved in 6 mL of water, poured into 36 mL of toluene solvent, bubbled for 15 minutes, and the solution was slowly injected into the two-necked flask through a syringe. The mixed solution was heated to 100°C under an argon atmosphere for 48 hours. After the reaction was completed and cooled to room temperature, the mixture was washed with water, extracted with chloroform, dried with magnesium sulfate, and distilled under reduced pressure to remove the organic solvent. Finally, the mixture was passed through a silica gel column with petroleum ether / dichloromethane (10:1) to obtain a yellow solid product 2,7-dithienylfluorene (LD-3) with a mass of 0.66 g. The yield of the reaction was 84%.

[0152] The structural confirmation data of the product are as follows:

[0153] Mass Spectrometry: EI:M + :330.

[0154] Mass spectrometry: MS (MALDI-TOF): calculated value M - ,330; measured value,330.

[0155] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ (ppm): 7.78 (m, 4H), 7.66 (d, 2H), 7.37 (s, 2H), 7.28 (d, 2H), 7.11 (m, 2H), 3.99 (s, 2H).

[0156] The spectral properties and electrochemical properties of the obtained yellow solid product are determined as follows:

[0157] (1) Spectral properties of LD-3

[0158] Figure 3 (a) is the UV-visible absorption spectrum of 2.7-dithienylfluorene in chloroform solution. As can be seen from the figure, the maximum absorption peak of LD-3 in chloroform solution is 349nm.

[0159] (2) Electrochemical properties of LD-3

[0160] The three-electrode system was used for testing: the working electrode was a glassy carbon electrode, the platinum wire was the counter electrode, the Ag / AgCl was the reference electrode, and Bu4NPF6 was the supporting electrolyte. The test conditions were: the scanning range was 0-1.6V (vs.Ag / AgCl), and the scanning rate was 100mV / s. Figure 3 (b) is the cyclic voltammetry curve of 2,7-dithiophenefluorene (LD-3) in chloroform solution. Electrochemical tests show that the initial oxidation potential of LD-3 is 1.08V, and the highest occupied orbital energy level (HOMO) calculated from this is -5.46eV.

[0161] Example 4: Preparation of 2.7-diquinolinylfluorene (LD-4)

[0162]

[0163] Add the reactants 2,7-dibromofluorene (1g, 3mmol), 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline (2.296g, 9mmol), tetrakistriphenylphosphine palladium (208mg, 0.06eq.) and phase transfer agent to a dry two-necked flask. Then, replace the inert gas three times through a vacuum oil pump-double-row tube, slowly add 30mL of toluene to the flask with a syringe, and potassium carbonate (3.3128g, 24mmol) dissolved in 12mL of water. The whole system is heated to 100°C under an argon atmosphere and stirred for 72 hours. After the reaction was completed and the mixture cooled to room temperature, 75 mL of chloroform solution was added for extraction. Magnesium sulfate was added to the organic phase for drying. The organic solvent was removed by distillation under reduced pressure. The mixture was passed through a silica gel column (petroleum ether: ethyl acetate = 3:2) to obtain a white product, 2.7-diquinolinylfluorene (LD-4), with a mass of 0.65 g and a yield of 50%.

[0164] The structural confirmation data of the product are as follows:

[0165] Mass Spectrometry: EI:M + :420.

[0166] Mass spectrometry: MS (MALDI-TOF): calculated value M - ,420; measured value,420.

[0167] H NMR spectrum: 1 H NMR (400MHz, CDCl3) δ (ppm): 8.95 (s, 2H), 8.32 (m, 4H), 8.13 (s, 4H), 7.97 (d, 4H), 7.80 (d, 2H), 7.51 (m, 2H), 4.12 (s, 2H).

[0168] The spectral properties, electrochemical properties and thermodynamic properties of the obtained white solid product were determined as follows:

[0169] (1) Spectral properties of LD-4

[0170] Figure 4(a) is the UV-visible absorption spectrum of 2.7-diquinolinylfluorene in chloroform solution. As can be seen from the figure, the maximum absorption peak of LD-4 in chloroform solution is 341nm.

[0171] (2) Electrochemical properties of LD-4

[0172] The three-electrode system was used for testing: the working electrode was a glassy carbon electrode, the platinum wire was the counter electrode, the Ag / AgCl was the reference electrode, and Bu4NPF6 was the supporting electrolyte. The test conditions were: the scanning range was 0-1.6V (vs.Ag / AgCl), and the scanning rate was 100mV / s. Figure 4 (b) is the cyclic voltammetry curve of 2,7-diquinolinylfluorene (LD-4) in chloroform solution. Electrochemical tests show that the initial oxidation potential of LD-4 is 1.35V, and the highest occupied orbital energy level (HOMO) calculated from this is -5.75eV.

[0173] Example 5: Controllable preparation of two crystalline phases of the compound (LD-1) prepared in Example 1

[0174] Crystal phase preparation process: Place the quartz boat filled with LD-1 powder in the high temperature zone of the tube furnace, place multiple OTS-modified SiO2 silicon wafers in the low temperature zone, introduce 35pa nitrogen at 155°C, and deposit for 2.5 hours to obtain organic single crystals with regular shapes. The crystals grown on the silicon wafer close to the heat source are flake-shaped, which we named α-phase LD-1 crystals; the crystals grown on the silicon wafer away from the heat source are stick-shaped, which we named β-phase LD-1 crystals.

[0175] The single crystal structure (orthorhombic system) of α-phase LD-1 is as follows Figure 5 shown.

[0176] The unit cell parameters are as follows: a = 5.8687 (2), α=90°, β=90°, γ=90°.

[0177] The single crystal structure (monoclinic system) of β-phase LD-1 is as follows Figure 6 shown.

[0178] The unit cell parameters are as follows: a = 7.9816 (3), α=90°, β=95.917(3)°, γ=90°.

[0179] Example 6: Preparation of organic field effect transistor devices using the compounds of the present invention and performance testing of the devices

[0180] Device preparation: Take the cleaned OTS-modified silicon wafer, put it into a tube furnace, evacuate it, pass argon gas, and obtain crystals of 2,7-diphenylfluorene (LD-1), 2,7-dinaphthylfluorene (LD-2), and 2,7-dithienylfluorene (LD-3) on the modified OTS silicon wafer by gas phase transport method. Finally, use the method of gold film (as source and drain) to prepare organic single crystal field effect devices under atmospheric conditions.

[0181] The structural diagram of the device model is shown in Figure 7 shown.

[0182] Device performance test: The above-mentioned organic single crystal field effect transistor device was placed on a Keithley 4200 micro-operation probe station to test the transfer curve and output curve respectively. The output curve refers to the transfer curve at a certain gate voltage V G Under this condition, the source-drain current I SD With source-drain voltage V SD The transfer curve refers to the change curve of the source-drain voltage V SD Under this condition, the source-drain current I SD With gate voltage V G Among them, the maximum single crystal hole mobility of α-phase 2,7-diphenylfluorene (LD-1) is 0.25 cm 2 V - 1 s -1 , switch ratio 10 6 , the threshold voltage is 5V. Figure 8 The typical transfer curve and output curve of the device are shown. The maximum single crystal hole mobility of β-phase 2,7-diphenylfluorene (LD-1) is 0.08 cm 2 V -1 s -1 , switch ratio 10 4 , the threshold voltage is -20V. Fig. 9 The typical transfer curve of the device is shown. The maximum single crystal hole mobility of 2,7-dinaphthylfluorene (LD-2) is 0.74 cm 2 V -1 s -1 , switch ratio 10 6 , the threshold voltage is 2.5V. Fig.10 The typical transfer curve and output curve of the device are shown. The maximum single crystal hole mobility of 2,7-dithienylfluorene (LD-3) is 2.14×10 -3 cm 2 V -1 s -1 , switch ratio 10 2 , the threshold voltage is -25V. Fig.11 Shown is a typical transfer curve of the device.

[0183] Example 7: Testing of the amplified spontaneous emission properties of the compound (LD-1) prepared in Example 1

[0184] The test of amplified self-emission phenomenon uses a third harmonic Nd:YAG pulse laser as pump light source, with a laser wavelength of 355nm, a pulse length of 10ns, and a frequency of 10Hz. A cylindrical mirror is used to change the light spot into a strip shape, an adjustable slit is used to adjust the length of the strip light spot, a neutral density attenuator is used to control the energy of the pump light source, and a power meter is used to test the energy of the pulse light source. Fig.12 As the pump energy increases, the half-peak width of the fluorescence spectrum of the LD-1 crystal gradually narrows, resulting in the phenomenon of amplified spontaneous emission, with a threshold of 168 μJ cm -2 , indicating that LD-1 crystal can be used as a gain medium in organic solid-state lasers.

[0185] Example 8: Performance test of the compound (LD-1) prepared in Example 1 in organic solid laser

[0186] A femtosecond laser light source with a wavelength of 355nm, a pulse width of 100fs, and a frequency of 1KHz was selected to excite the middle position of a single LD-1 crystal on a two-dimensional optical platform. The fluorescence of the LD-1 crystal was collected by moving the lens of the objective lens. The collected signal was directly reflected and converged to the spectrometer, thereby obtaining the spatial resolution spectrum of a single LD-1 crystal, such as Fig.13 As shown, with the increase of pump energy, the spectrum gradually narrows, and finally the laser mode peak appears and the laser is generated.

[0187] Example 9: Preparation of horizontal organic light-emitting field effect transistors using the compounds of the present invention and performance testing of the transistors

[0188] Preparation of the device: Take the cleaned SiO2 / Si as the substrate, spin-coat polymethyl methacrylate (PMMA) as the buffer layer, keep annealing at 90℃ for 2 hours, transfer the LD-2 organic single crystal to this substrate, and then perform asymmetric electrode evaporation in the glove box, including gold (30nm) / molybdenum trioxide (2nm) calcium (35nm) / cesium fluoride (0.6nm).

[0189] Microscope photos of the device are shown in Fig.14 shown.

[0190] Device performance test: In a glove box, the horizontal organic light-emitting field effect transistor device was transferred to a Keithley 4200 micro-operation probe station to test its transfer curve and output curve. The optical test was completed by a photomultiplier tube. Fig.15 Shown are the electroluminescence curves of the device at different gate voltages.

[0191] Example 10: Preparation of vertical organic light-emitting field effect transistors using the compounds of the present invention and performance testing of the transistors

[0192] Preparation of the device: A gold electrode was deposited on a graphene substrate patterned on SiO2 / Si. The substrate was placed in a glove box and charged at a speed of about 3A / s and 6×10 -4 200nm N,N'-diphenyl-N,N'-(1-naphthyl)-1,1'-biphenyl-4,4'-diamine, 40nm LD-1 and 40nm 1,3,5-tri[(3-pyridyl)-phenyl-3-yl]benzene were vacuum-deposited at a pressure of 1.5 pa. After the organic layer was evaporated, the top electrode was evaporated in a glove box, and 0.5nm lithium fluoride, 1nm aluminum and 38.5nm silver were deposited at a speed of 0.1A / s.

[0193] The luminescence microscope photo of the device model is shown in Fig.16 shown.

[0194] Device performance test: In a glove box, the vertical organic light-emitting field effect transistor device was transferred to a Keithley 4200 micro-operation probe station to test its transfer curve and output curve. The optical test was completed by a photomultiplier tube. Fig.17 Shown are the typical current density curve of the device and its electroluminescence curve at different gate voltages.

[0195] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A compound having a structure as shown in the following formula (I): in, The two R are the same or different, and each R is independently selected from unsubstituted or optionally substituted by one, two, three or more R a Substituted with the following groups: C 10-14 Aryl, 10-14 membered heteroaryl; Among them, each R a are independently selected from C 1-6 alkyl Both R1 are selected from hydrogen.

2. The compound according to claim 1, characterized in that In the compound of formula (I), Two R are the same or different, and each R is independently selected from the following groups: naphthyl, anthracenyl, quinolyl, isoquinolyl, dithienyl, trithienyl, tetrathienyl, 2-(2-ethylhexyl)-1H-benzoisoquinoline-1,3(2H)-dione; Both R1 are selected from hydrogen.

3. The compound according to claim 1 or 2, characterized in that The compound of formula (I) is selected from the following compounds:

4. A method for preparing a compound of formula (I) according to any one of claims 1 to 3, which is one of the following methods: Method (a): Compound A is reacted with compound RB(OR')2 to obtain a compound of formula (I): in, R and R1 have the meanings as described in any one of claims 1 to 3, X is fluorine, chlorine, bromine or iodine; two R's are the same or different and are independently selected from hydrogen, C 1-6 Alkyl, or two R' together with the O atom to which they are attached and the B atom form a 5-10 membered ring; Method (b): comprising the following steps: Step (1): Compound A is reacted with compound bis(pinacol)diboron to obtain compound C-1: Step (2): reacting compound C-1 with compound RX to obtain a compound of formula (I): wherein R and R1 have the meanings as described in any one of claims 1 to 3, and X is fluorine, chlorine, bromine or iodine; or, Method (c): Compound C-2 is reacted with compound RX to obtain a compound of formula (I): Wherein, R and R1 have the definitions as described in any one of claims 1 to 3, and X is fluorine, chlorine, bromine or iodine.

5. The preparation method according to claim 4, characterized in that: The reaction of method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) are carried out in the presence of a base, wherein the base is one, two or more of sodium carbonate, cesium carbonate, or potassium carbonate; The reaction of method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) are carried out in the presence of a catalyst, which is a palladium catalyst; In the method (a), the compound RB(OR')2 is One of the above, wherein R has the definition as described in any one of claims 1 to 3; The reaction of method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) are carried out in an organic solvent, wherein the solvent is one, two or more of methanol, ethanol, tetrahydrofuran, dimethyl sulfoxide, ethylene glycol dimethyl ether, dimethylformamide, toluene, or dioxane; The reaction of method (a), the reaction of steps (1) and (2) of method (b), and the reaction of method (c) are carried out under the protection of an inert gas, which is a gas inert to the reaction.

6. The preparation method according to claim 5, characterized in that: The palladium catalyst is one, two or more of tetrakistriphenylphosphine palladium, PdCl2(dppf)2 or Pd(OAc)2; The compound RB(OR')2 is phenylboronic acid, 2-naphthaleneboronic acid or 6-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)quinoline; The inert gas is nitrogen or argon.

7. Use of the compound of formula (I) or the following compound as claimed in any one of claims 1 to 3 as an organic semiconductor material in an organic optoelectronic device; Preferably, the organic semiconductor material is a thin film and / or crystal of multiple crystal phases obtained by physical vapor deposition; Preferably, the organic semiconductor material is used in the preparation of organic field effect transistors, organic light-emitting field effect transistors, organic photo-controlled transistors and / or organic light-emitting diodes and related functional devices, as well as in organic solid-state lasers and related functional devices.

8. An organic field effect transistor, comprising a compound of formula (I) according to any one of claims 1 to 3 or the following compound: Preferably, the semiconductor layer of the organic field effect transistor comprises a compound of formula (I) or the following compound: Preferably, the semiconductor layer is an organic thin film layer and / or an organic single crystal layer; Preferably, the organic field effect transistor comprises an organic thin film field effect transistor and / or an organic single crystal field effect transistor; Preferably, the organic field effect transistor comprises a P-type organic field effect transistor, an N-type organic field effect transistor and / or a bipolar organic field effect transistor.

9. An organic solid-state laser comprising a compound of formula (I) as described in any one of claims 1 to 3 or the following compound: Preferably, the gain medium of the organic solid laser comprises a compound of formula (I); Preferably, the gain medium is an organic thin film layer and / or an organic single crystal layer and / or a solution; Preferably, the organic solid laser includes an organic thin film laser and / or an organic single crystal laser and / or an organic solution laser.

10. An organic light-emitting field-effect transistor, comprising a compound of formula (I) according to any one of claims 1 to 3 or the following compound: Preferably, the organic light emitting field effect transistor is a horizontal organic light emitting field effect transistor or a vertical organic light emitting field effect transistor; Preferably, the semiconductor layer of the horizontal and vertical organic light-emitting field-effect transistors comprises a compound of formula (I) as claimed in any one of claims 1 to 3 or the following compound: Preferably, the semiconductor layer is an organic thin film layer and / or an organic single crystal layer; Preferably, the horizontal organic light emitting field effect transistor comprises a horizontal organic thin film light emitting field effect transistor and / or a horizontal organic single crystal light emitting field effect transistor; Preferably, the vertical organic light emitting field effect transistor comprises a vertical organic thin film light emitting field effect transistor and / or a vertical organic single crystal light emitting field effect transistor.

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