CN112661743B - Naphthothiodibenzofuran-based green light micromolecule and preparation method and application thereof - Google Patents
Naphthothiodibenzofuran-based green light micromolecule and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic photoelectricityIn particular to a green light micromolecule based on naphthothiodibenzofuran, a preparation method thereof and application thereof in an Organic Light Emitting Diode (OLED). The chemical structure of the naphtho-sulfur dibenzofuran-based green-light micromolecule is shown as follows, the naphtho-sulfur dibenzofuran-based green-light micromolecule is obtained by taking anthracene group with high fluorescence quantum yield as a core based on electron donor naphtho-sulfur dibenzofuran and electron acceptor naphtho-sulfur dibenzofuran, through reasonable molecular design, not only can high solid-state luminous efficiency be realized, but also the exciton utilization rate can be improved through a hybridization local-charge transfer (HLCT) mechanism, the naphtho-sulfur dibenzofuran-based green-light micromolecule is used as a luminous layer in a non-doped or doped Organic Light Emitting Diode (OLED), the prepared device has the characteristics of high efficiency, low driving voltage and the like, and the problems of low efficiency of the traditional fluorescent material and serious roll-off of the device efficiency under high brightness are effectively solved.
Description
Technical Field
The invention belongs to the technical field of organic photoelectricity, and particularly relates to a green light micromolecule based on naphthothiodibenzofuran, and a preparation method and application thereof.
Background
Organic materials are adopted as luminescent materials in an Organic Light Emitting Diode (OLED) display, the material structure is easy to modify and improve, and the selection range is wide; the driving voltage is low, and only 3-12V direct current voltage is needed; self-luminous without backlight source; wide viewing angle, approaching 180 °; the response speed is high and can reach 1 mu s magnitude; in addition, the flexible panel has the advantages of light weight, ultrathin thickness, large size, simple and convenient forming and processing, and the like. Due to the numerous advantages of OLED displays, there has been a great deal of interest in the scientific and industrial fields, and since the development of OLED devices by kodak corporation in the united states in 1987, there have been many organizations investing resources into the development of OLED technology. With the rapid development of decades, the OLED flat panel display technology has become mature and has occupied a place in the flat panel display field, but still needs to be improved in terms of lifetime, stability, cost, etc.
According to spin statistics, the combination of electrons and holes forms excitons, which will yield 25% singlet excitons and 75% triplet excitons. Singlet state (S) 1 ) And triplet (T) 1 ) Radiative transition of excitons back to ground state (S) 0 ) And simultaneously emits light with different properties,namely fluorescence and phosphorescence. Singlet excitons of conventional fluorescent materials are from S 1 State to S 0 The state is emitted by fast radiation transition, the time scale is nanosecond, and T is 1 The excitons in the state return to the ground state in a non-radiative deactivation mode due to the spin forbidden effect and then are dissipated in a heat and other modes, so that the internal quantum efficiency of the device is only 25% at most theoretically, the external quantum efficiency is only 5% at most correspondingly, and the improvement of the device performance is severely limited. In view of the key role of organic electroluminescent materials in OLED display technology and the urgent need of cost reduction, the industry is actively investing in developing new generation of OLED materials with high energy utilization efficiency and low cost, and has made significant progress and breakthrough. The main research and development directions include: triplet-triplet quenching delayed fluorescence (TTA), thermally excited delayed fluorescence (TADF) and local hybrid charge transfer states (HLCT). The TTA converts a large proportion of T excitons into S excitons in an intersystem crossing mode, extra fluorescence is generated, namely two triplet excitons are quenched to generate an extra singlet exciton and a ground state, the extra singlet exciton is radiated and de-excited to emit extra fluorescence, the internal quantum efficiency of the fluorescence can exceed 25% of the theoretical limit, and the high exciton utilization rate is shown. However, the material for realizing the high-efficiency electroluminescent performance by utilizing the TTA mechanism is mostly based on an anthracene system, and has poor universality; another electroluminescent material based on the TADF mechanism can obtain excellent lumen efficiency and internal quantum efficiency, but at high current density, the device efficiency decays relatively fast, and the industrial application is not easy, so it is necessary to develop an electroluminescent material with high exciton utilization rate and slow efficiency decay.
Disclosure of Invention
The invention aims at providing a green light small molecule based on naphtho-sulfur dibenzofuran aiming at the current organic/monomer light-emitting diode (O/PLED). The electroluminescent material has good thermal stability and excellent photoelectric property, is suitable for solution processing technologies such as spin coating and ink-jet printing, and has great application potential.
The invention also aims to provide a preparation method of the naphthothiodibenzofuran-based green-light small molecule.
The invention further aims to provide application of the naphthothiodibenzothiophene-based green light micromolecules, and the electroluminescent monomer can be used for light-emitting diodes, organic field effect transistors, organic solar cells, organic laser diodes and the like.
The purpose of the invention is realized by the following technical scheme:
a green light micromolecule based on naphtho-sulfur dibenzofuran has a chemical structural formula shown as a formula (I):
wherein R is one of a straight-chain alkyl group having 1 to 20 carbon atoms, a branched or cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched or cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkenyl group having 2 to 20 carbon atoms, a branched or cyclic alkenyl group having 3 to 20 carbon atoms, a straight-chain alkynyl group having 2 to 20 carbon atoms, a branched or cyclic alkynyl group having 3 to 20 carbon atoms, a straight-chain alkylcarbonyl group having 2 to 20 carbon atoms, and a branched or cyclic alkylcarbonyl group having 3 to 20 carbon atoms.
Preferably, R is methyl.
The preparation method of the green light micromolecule based on the naphtho-dibenzothiophene comprises the following steps:
(1) In an inert gas environment, completely dissolving 9-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene and pinacol borate in a solvent, and reacting under the action of a catalyst and alkali to obtain 2- (7,7-dialkyl-7H-benzo [ c ] fluorene) -4,4,5,5-tetramethyl-1,3,2-dioxaborane;
(2) Under the inert gas environment, 2- (7,7-dialkyl-7H-benzo [ c ] fluorene) -4,4,5,5-tetramethyl-1,3,2-dioxaborane and 4-bromo-2- (ethylsulfinyl) -1-iodobenzene are completely dissolved in a solvent, and are subjected to temperature rise reaction under the action of a catalyst, alkali and tetrabutylammonium bromide to obtain a compound 9- (4-bromo-2- (ethylsulfinyl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene;
(3) Dissolving a compound 9- (4-bromo-2- (ethylsulfinyl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene in a solvent under an ice bath condition, then adding phosphorus pentoxide to react, adding obtained reaction liquid into ice water after the reaction, filtering to obtain filter residue, completely dissolving the filter residue into pyridine after the filter residue is dried, and carrying out reflux reaction in an inert gas environment to obtain a compound 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene;
(4) Dissolving a compound 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene in a solvent under an inert gas environment, and reacting under the action of an oxidant hydrogen peroxide to obtain 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene 13,13-dioxide;
(5) Under the inert gas environment, 11-bromine-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene, p-phenylboronic acid pinacol ester and tetrabutylammonium bromide are dissolved in a solvent and undergo a suzuki coupling reaction under the action of a catalyst and alkali to obtain a compound 2- (4- (7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophen-11-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborane;
(6) Dissolving 2- (4- (7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophen-11-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborane, 9,10-dibromoanthracene and tetrabutylammonium bromide in a solvent under an inert gas environment, and performing suzuki coupling reaction under the action of a catalyst and alkali to obtain a compound 11- (4- (10-bromoanthracene-9-yl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene;
(7) Under inert gas atmosphere, compounds 11- (4- (10-bromoanthracene-9-yl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene, 1,3-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) benzene and tetrabutylammonium bromide are dissolved in a solvent, and a suzuki coupling reaction is carried out under the action of a catalyst and alkali to obtain a compound 2- (3- (10- (4- (7,7-dialkyl-7H-benzo [ c ] fluorenyl [2,3-d ] thiophene-11-yl) phenyl ] anthracene-9-yl)) -4,4,5,5-tetramethyl-1,3,2-dioxaborane;
(8) Under inert gas atmosphere, the compound 2- (3- (10- (4- (7,7-dialkyl-7H-benzo [ c ] fluorenyl [2,3-d ] thiophen-11-yl) phenyl ] anthracene-9-yl)) -4,4,5,5-tetramethyl-1,3,2-dioxaborane and 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene 13,13-dioxide are completely dissolved in a solvent, and suzuki coupling reaction is carried out under the action of a catalyst and alkali to obtain a final product 11- (3- (10- (4- (7,7-dimethyl-7H-benzo [ b ] benzo [ 3724 zft 3724 ] fluorenyl [2,3-d ] thiophen-11-yl) phenyl ] anthracene-9-yl) phenyl) -6242-dimethyl-6242H-8542 zxft [ c ] anthracene-9-yl ] dibenzo-9843-85zxft 9843-benzo [ b ] fluorene.
The preparation route of the green light micromolecule based on naphtho-dibenzothiane is as follows:
the solvent in the step (1) is at least one of 1,4-dioxane, toluene and N, N-dimethylformamide, and is preferably 1,4-dioxane.
The catalyst in the step (1) is at least one of [1,1 '-bis (diphenylphosphino) ferrocene ] palladium dichloride and palladium acetate, preferably [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride;
the alkali in the step (1) is at least one of potassium acetate, sodium acetate, potassium formate or sodium formate, preferably potassium acetate;
the reaction in step (1) means a reaction at 60 to 120 ℃ for 2 to 10 hours, preferably at 90 ℃ for 6 hours. The method also comprises a purification step after the reaction is finished, and the method comprises the following specific steps: cooling the obtained reaction solution to room temperature, extracting with dichloromethane and water, drying with anhydrous magnesium sulfate, concentrating the solution to obtain gray black liquid, purifying by silica gel column chromatography, and eluting with petroleum ether/dichloromethane mixed solvent (6/1,v/v) to obtain white solid.
In the step (1), the molar ratio of 9-bromine-7,7-dialkyl-7H-benzo [ c ] fluorene, pinacol borate, catalyst and alkali is 1:1-3; preferably 1.5;
the solvent in the step (2) is at least one of toluene, xylene and tetrahydrofuran, and is preferably toluene;
the catalyst in the step (2) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium, and preferably tetrakistriphenylphosphine palladium;
the alkali in the step (2) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, preferably potassium carbonate;
the temperature-rising reaction in the step (2) refers to the reaction for 24 to 72 hours when the temperature rises to 40 to 80 ℃, and preferably the reaction for 36 hours at 60 ℃.
In the step (2), the molar ratio of 2- (7,7-dialkyl-7H-benzo [ c ] fluorene) -4,4,5,5-tetramethyl-1,3,2-dioxaborane, 4-bromo-2- (ethylsulfinyl) -1-iodobenzene, catalyst, alkali and tetrabutylammonium bromide is 1:1-3; preferably 1.5;
in step (3), the ice bath conditions are-20 to 10 ℃, preferably 0 ℃.
The solvent in the step (3) is at least one of trifluoromethanesulfonic acid and trifluoroacetic acid, and preferably trifluoroacetic acid;
the molar ratio of the 9- (4-bromo-2- (ethylsulfinyl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene and phosphorus pentoxide in step (3) is 1:5-10, preferably 1:5;
the time for adding the solvent and the phosphorus pentoxide to react in the step (3) is 4-12h, preferably 8h; the reflux reaction in the inert gas environment in the step (3) refers to a reaction at 110 ℃ for 12 hours in the inert gas environment.
The pyridine in the step (3) is used as a solvent and is used as a reaction medium, so that the reaction dosage is not limited.
The solvent in the step (4) is at least one of acetic acid, formic acid and concentrated sulfuric acid, and acetic acid is preferred; the mass fraction of the hydrogen peroxide in the step (4) is 20-50 wt%, preferably 35%; the ratio of the molar quantity of the 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene to the volume of the hydrogen peroxide in the step (4) is 1mmol to 5mL, preferably 1mmol;
the reaction in the step (4) is carried out at room temperature for 12-36h, preferably 24h.
The solvent in the step (5) is at least one of toluene, xylene and chlorobenzene, and toluene is preferred; the catalyst in the step (5) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium, and is preferably tetrakistriphenylphosphine palladium; the alkali in the step (5) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, preferably potassium carbonate; tetrabutylammonium bromide used as a phase transition catalyst in the step (5).
The reaction in the step (5) is carried out at 60-120 ℃ for 12-36h, preferably at 90 ℃ for 24h.
In the step (5), the molar ratio of 9,11-dibromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene, p-benzenediboronic acid pinacol ester, catalyst, alkali and tetrabutylammonium bromide is 1:1-3; preferably 1.1;
the solvent in the step (6) is at least one of toluene, xylene and chlorobenzene, and toluene is preferred; the catalyst in the step (6) is at least one of tetratriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium, and preferably tetratriphenylphosphine palladium; the alkali in the step (6) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, preferably potassium carbonate; tetrabutylammonium bromide in the step (6) is used as a phase transfer catalyst.
The reaction in the step (6) means a reaction at 60 to 120 ℃ for 12 to 36 hours, preferably a reaction at 90 ℃ for 24 hours.
In the step (6), the molar ratio of 2- (4- (9-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophen-11-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborane, 9,10-dibromoanthracene, catalyst, potassium carbonate and tetrabutylammonium bromide is 1:1-3; preferably 1.5;
the solvent in the step (7) is at least one of toluene, xylene and chlorobenzene, and toluene is preferred; the catalyst in the step (6) is at least one of tetratriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium, and preferably tetratriphenylphosphine palladium; the alkali in the step (6) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, preferably potassium carbonate; tetrabutylammonium bromide in the step (6) is used as a phase transfer catalyst.
The reaction in the step (7) means a reaction at 60 to 120 ℃ for 12 to 36 hours, preferably a reaction at 90 ℃ for 24 hours.
In the step (7), the molar ratio of 11- (4- (10-bromoanthracene-9-yl) phenyl) -9-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene, pinacol ester of m-phenyl diboronic acid, catalyst, alkali and tetrabutylammonium bromide is 1:1-3; preferably 1;
the solvent in the step (8) is at least one of toluene, xylene and chlorobenzene, and toluene is preferred; the catalyst in the step (6) is at least one of tetratriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium, and preferably tetratriphenylphosphine palladium; the alkali in the step (6) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, preferably potassium carbonate;
the reaction in the step (8) means a reaction at 60 to 120 ℃ for 12 to 36 hours, preferably a reaction at 90 ℃ for 24 hours.
In step (8), the molar ratio of 2- (3- (10- (4- (9-bromo-7,7-dialkyl-7H-benzo [ c ] fluorenyl [2,3-d ] thiophen-11-yl) phenyl ] anthracene-9-yl)) -4,4,5,5-tetramethyl-1,3,2-dioxaborane, 11-bromo-9-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene 13,13-dioxide, catalyst, base and tetrabutylammonium bromide is 1:1-3 to 0.03-0.1, preferably 1.
The green light micromolecule based on naphtho-dibenzothiophene is applied to preparing light-emitting layers of devices such as light-emitting diodes, organic field effect transistors, organic solar cells, organic laser diodes and the like, and is preferably applied to preparing the light-emitting layers of the light-emitting diode devices.
The naphthodibenzothiane-based green light micromolecules can be independently used as a non-doped device luminescent layer material, and can also be used as a doped device luminescent layer material together with a doped parent, wherein the doped parent is mCP or mADN, and the mass percentage of the doped parent mCP or mADN in the luminescent layer material is 80-99%; preferably 80% to 95%.
Further, the application of the naphthodibenzothiane-based green light small molecule in preparing a light emitting layer of a light emitting diode, an organic field effect transistor, an organic solar cell, an organic laser diode and other devices specifically comprises the following steps: dissolving the green light micromolecules based on naphtho-dibenzothiophene with an organic solvent (the concentration of the green light micromolecules based on naphtho-dibenzothiophene is 20-30 mg/mL), and preparing a non-doped device by spin coating, ink-jet printing or printing film forming; or dissolving the doped parent substance and the green light micromolecules based on the naphtho-dibenzothiophene by using an organic solvent (the total concentration of the doped parent substance and the green light micromolecules based on the naphtho-dibenzothiophene is 20-30 mg/mL), and preparing the doped device by spin coating, ink-jet printing or printing film forming, wherein the mass percentage of the doped parent substance mCP or mADN is 80-99%. Preferably 85% -95%;
further, the organic solvent is at least one of tetrahydrofuran, chloroform, toluene, xylene and chlorobenzene;
further, the thickness of the light emitting layer is 10 to 1000nm.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The naphtho-dibenzothiophene-based green light micromolecule contains sulfur heteroatoms, so that the hole transport capability of the material can be improved; the material contains sulfone group and anthracene group, which can obviously improve the fluorescence quantum yield of the luminescent material; the green light micromolecule multi-element ring-combining unit has good planarity, is favorable for the transmission of current carriers and is favorable for an electroluminescent device to obtain high-efficiency and stable electroluminescent performance;
(2) The naphtho-dibenzothiophene-based green light micromolecules have the characteristics of hybridization local-charge transfer (HLCT), can greatly improve the exciton utilization rate, and the prepared electroluminescent device has the characteristics of lower driving voltage, higher current efficiency and external quantum efficiency and obtains excellent electroluminescent performance;
(3) The green-light micromolecules based on naphtho-dibenzothiophene prepared by the invention have the advantages of low raw material price, simple and convenient synthetic route, convenient purification and contribution to industrial large-scale production.
(4) The naphtho-dibenzothiophene-based green light micromolecule has better solubility, is suitable for solution processing, can reduce the preparation cost of devices, and can be used for preparing large-area flexible OLED devices.
Drawings
Fig. 1 is a graph of the thermogravimetric loss of compound GH 1.
FIG. 2 is a graph of the ultraviolet-visible absorption spectrum and the fluorescence spectrum of a compound GH1 in a thin film state.
FIG. 3 is a graph of Stokes shift of compound GH1 in different solvents as a function of solvent polarizability.
Fig. 4 is a graph of current efficiency versus current density for an undoped device based on compound GH 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto. The examples, in which specific conditions are not specified, were carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
1. Preparation of target compound GH1
(1) Preparation of 2- (7,7-dialkyl-7H-benzo [ c ] fluorene) -4,4,5,5-tetramethyl-1,3,2-dioxaborane
9-bromo-7,7-dialkyl-7H-benzo [ c ] in a 500mL two-necked flask under an argon atmosphere]Fluorene (16.16g, 50mmol), pinacol ester of boronic acid (19.06g, 75mmol) and potassium acetate (24.53g, 0.25mol) were dissolved in 200mL 1,4-dioxane, purged three times, and added with catalyst [1,1' -bis (diphenylphosphino) ferrocene]Palladium dichloride (1.83g, 2.5 mmol), vacuumizing for three times, heating to 90 ℃, refluxing, reacting for 6 hours, stopping the reaction, cooling to room temperature, extracting with dichloromethane and water, drying with anhydrous magnesium sulfate, concentrating the solution to obtain a gray black liquid, purifying by silica gel column chromatography, and using a mixed solvent of petroleum ether and dichloromethane (6/1,v/v) as an eluent to obtain a white solid with the yield of 76%. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(2) Preparation of 9- (4-bromo-2- (ethylsulfinyl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene
In a 500mL two-neck bottle under argon atmosphere, first 2- (7,7-dialkyl-7H-benzo [ c)]Fluorene) -4,4,5,5-tetramethyl-1,3,2-dioxaborane (18.5 g, 50mmol), 4-bromo-2- (ethylsulfinyl) -1-iodobenzene (19.75g, 75mmol) and tetrabutylammonium bromide (805.9 mg,2.5 mmol) were dissolved in 250mL of toluene, 50% by weight aqueous potassium carbonate (34.5 g/34.5mL deionized water, 0.25 mol) was added, the gas was purged three times, the catalyst tetratriphenylphosphine palladium (2.89g, 2.5 mmol) was added rapidly under the protection of argon gas, the gas was purged three times, the temperature was raised to 60 ℃ for reaction for 36h, the reaction was stopped, the solution was cooled to room temperature, the solution was concentrated and dried, then dichloromethane and water were extracted and anhydrous magnesium sulfate was used to concentrate the solution to obtain a yellow liquid, the yellow liquid was purified by silica gel column chromatography, and the mixed solvent of petroleum ether/dichloromethane (4/1,v/v) was used as a white solid in a yield of 72%. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(3) Preparation of 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene
9- (4-bromo-2- (ethylsulfinyl) phenyl) -7,7-dialkyl-7H-benzo [ c ] in a 500mL two-necked flask at 0 deg.C]Dissolving fluorene (9.5 g, 0.02mol) in 60mL of trifluoroacetic acid, adding phosphorus pentoxide (14.19g, 0.1mol), exhausting and changing gas for three times, reacting for 8h, stopping the reaction, adding the solution into ice water to quench, filtering to obtain filter residue, adding the filter residue into 250mL of pyridine after the filter residue is dried in the air, heating to 110 ℃ in an argon gas environment, refluxing by heating, reacting for 12h, stopping the reaction, cooling to room temperature, adding concentrated hydrochloric acid to neutralize the pyridine, extracting with dichloromethane and water, drying with anhydrous magnesium sulfate, concentrating the solution, and then adding the concentrated solution into a containerThe yellow liquid is obtained and purified by silica gel column chromatography, and petroleum ether is used as eluent, so that light yellow solid is obtained with the yield of 36 percent. 1 H NMR、 13 The CNMR, MS and element analysis results show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(4) Preparation of 11-bromo-7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene 13,13-dioxide
In a 500mL two-necked flask, under an argon atmosphere, 11-bromo-7,7-dialkyl-7H-benzo [ c ] was placed]Fluorene [2,3-d]Thiophene (8.58g, 20mmol) is dissolved in 50mL of hydrogen peroxide (35 percent of mass fraction) and 30mL of acetic acid, gas is pumped for three times, the mixture is stirred at room temperature, the reaction is stopped after 24 hours, dichloromethane and water are used for extraction, anhydrous magnesium sulfate is used for drying, the solution is concentrated to obtain yellow liquid, the yellow liquid is purified through silica gel column chromatography, petroleum ether is used as an eluent, yellow solid is obtained, and the yield is 81 percent. 1 H NMR、 13 The CNMR, MS and element analysis results show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(5) Preparation of 2- (4- (7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophen-11-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborane
In a 500mL two-mouth bottle under argon atmosphere, 11-bromine-7,7-dialkyl-7H-benzo [ c ] is firstly put]Fluorene [2,3-d]Thiophene (8.58g, 20mmol), p-benzenediboronic acid pinacol ester (7.26g, 22mmol) and tetrabutylammonium bromide (0.32g, 1mmol) are dissolved in 150mL of toluene, potassium carbonate aqueous solution with the mass fraction of 50% (13.8 g/13.8mL of deionized water, 0.1 mol) is added, gas is pumped for three times, catalyst tetratriphenylphosphine palladium (1.65g, 1.0mmol) is quickly added under the protection of argon gas, gas is pumped for three times, the temperature is increased to 90 ℃, heating and refluxing are carried out, the reaction is carried out for 24 hours, and the reaction is stoppedCooling to room temperature, concentrating the solution to remove toluene, extracting with dichloromethane and water, drying with anhydrous magnesium sulfate, concentrating the solution to obtain yellow liquid, purifying by silica gel column chromatography, and eluting with petroleum ether/dichloromethane mixed solvent (5/1,v/v) to obtain pale yellow solid with yield of 74%. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(6) Preparation of 11- (4- (10-bromoanthracen-9-yl) phenyl) -7,7-dialkyl-7H-benzo [ c ] fluorene [2,3-d ] thiophene
In a 500mL two-necked flask, under an argon atmosphere, 2- (4- (7,7-dialkyl-7H-benzo [ c ] is first placed]Fluorene [2,3-d]Thiophene-11-yl) phenyl) -4,4,5,5-tetramethyl-1,3,2-dioxaborane (11.05g, 20mmol), 9,10-dibromoanthracene (8.34g, 30mmol) and a phase transfer catalyst tetrabutylammonium bromide (0.32g, 1.0mmol) are dissolved in 180mL of toluene, a 50% by mass potassium carbonate aqueous solution (13.8 g/13.8mL of deionized water, 0.1 mol) is added, gas is pumped for three times, a catalyst tetratriphenylphosphine palladium (1.116g, 1.0mmol) is rapidly added under the protection of argon gas, gas is pumped for three times, the temperature is increased to 90 ℃ for 24 hours, the reaction is stopped, the mixture is cooled to room temperature, the toluene is removed, dichloromethane and water are extracted again, anhydrous magnesium sulfate is used for drying, the solution is concentrated to obtain a yellow liquid, the yellow liquid is purified by silica gel column chromatography, and a mixed solvent of petroleum ether/dichloromethane (5/1,v) is used as an eluent, and the yield is 66%. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(7) Preparation of 2- (3- (10- (4- (7,7-dialkyl-7H-benzo [ c ] fluorenyl [2,3-d ] thiophen-11-yl) phenyl ] anthracen-9-yl)) -4,4,5,5-tetramethyl-1,3,2-dioxaborane
In a 500mL two-mouth bottle under the argon atmosphere, firstly 11- (4- (10-bromoanthracene-9-yl) phenyl) -7,7-dialkyl-7H-benzo [ c)]Fluorene [2,3-d]Thiophene (13.63g, 20mmol), 1,3-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) benzene (8.26g, 30mmol) and a phase transfer catalyst tetrabutylammonium bromide (0.32g, 1.0mmol) are dissolved in 250mL of toluene, a 50% by mass potassium carbonate aqueous solution (13.8 g/13.8mL of deionized water, 0.1 mol) is added, gas is pumped for three times, a catalyst tetratriphenylphosphine palladium (1.116g, 1.0mmol) is rapidly added under the protection of argon gas, gas is pumped for three times, the temperature is increased to 90 ℃ for reaction for 24 hours, the reaction is stopped, the solution is cooled to the room temperature, the solution is concentrated to remove the toluene, dichloromethane is extracted with water and dried by magnesium sulfate, the solution is concentrated to obtain a yellow solid, the yellow solid is purified by silica gel column chromatography, and a mixed solvent of petroleum ether/dichloromethane (3/1,v) is used as a leaching yield of 61%. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
(8) Synthesis of target compound GH1
2- (3- (10- (4- (7,7-dialkyl-7H-benzo [ c ]) in a 500mL two-necked flask under an argon atmosphere]Fluorenyl [2,3-d]Thien-11-yl) phenyl]Anthracen-9-yl)) -4,4,5,5-tetramethyl-1,3,2-dioxaborane (8.04g, 10mmol), 11-bromo-7,7-dialkyl-7H-benzo [ c]Fluorene [2,3-d]Dissolving thiophene 13,13-dioxide (4.61g, 10mmol) and tetrabutylammonium bromide (0.16g, 0.5mmol) in 200mL of toluene, adding 50% by mass of potassium carbonate aqueous solution (6.9 g/6.9mL of deionized water and 50 mmol), vacuumizing for three times, quickly adding catalyst tetratriphenylphosphine palladium (0.578g, 0.5mmol) under the protection of argon, vacuumizing for three times, reacting at 90 ℃ for 24 hours, stopping the reaction, cooling to room temperature, removing toluene, extracting with dichloromethane and water, drying with anhydrous magnesium sulfate, concentrating the solution, and removing the tolueneThe yellow solid obtained is purified by silica gel column chromatography, and the mixed solvent of petroleum ether and dichloromethane (4/1,v/v) is eluent, so that light yellow solid is obtained with the yield of 54 percent. 1 H NMR、 13 The results of CNMR, MS and element analysis show that the obtained compound is a target product, and the chemical reaction equation of the preparation process is as follows:
the thermal weight loss (TG) curve of the electroluminescent material GH1 is shown in fig. 1. As can be seen from the figure, the electroluminescent material GH1 only undergoes a thermal decomposition process in the whole heating process, namely a thermal decomposition process of the conjugated main chain. When the mass of the electroluminescent material GH1 is reduced by 5%, the corresponding temperature is 498 ℃, i.e. the thermal decomposition temperature of the electroluminescent material GH1 is 498 ℃. The excellent thermal decomposition temperature benefits from the rigid structure of the material, which shows that the material has excellent heat resistance and can meet the practical requirement of the material.
The ultraviolet visible absorption spectrum and the fluorescence emission spectrum of the electroluminescent material GH1 in the thin film state are shown in FIG. 2, and it can be seen from FIG. 2 that the maximum absorption peak of the electroluminescent material GH1 in the thin film state is 441nm, the absorption peak is attributed to the charge transfer state of the material, and the maximum absorption peak at 374nm is attributed to the absorption of the conjugated skeleton. The strongest emission peak of the electroluminescent material GH1 is at 522nm, in the green region. The fluorescence quantum yield of the electroluminescent material GH1 in a toluene solution and a thin film state is tested by using a C11347 type quantum yield spectrometer of Hamamatsu company, wherein the concentration of the toluene solution is 1 multiplied by 10 -5 mol/L. The fluorescence quantum yield of GH1 in toluene is 95.2% through testing; the fluorescence quantum yield in the thin film state is 82.4%, with excellent fluorescence quantum yield, which is benefited by the presence of anthracene groups and sulfone groups with high fluorescence quantum yield.
According to molecular structure analysis, the naphthothiofluorene unit and the naphthothiofluorene unit are connected through benzene-anthracene as a pi bridge, but the naphthothiofluorene unit and an adjacent phenyl are connected through a meta position, and the naphthothiofluorene unit and the adjacent phenyl have a certain torsion angle. The Stokes shift of the compound GH1 in different polar solvents is plotted against the solvent polarizability as shown in FIG. 3. When the polarization rate f is less than or equal to 0.15, the slope of the curve is smaller, which indicates that the compound GH1 shows typical local excited state luminescence characteristics in a low-polarity (polarization rate f is less than or equal to 0.15) solvent, while in a medium-polarity solvent, ethyl ether (f = 0.17), the Charge Transfer (CT) component in a molecular excited state begins to stand out, and when the polarization rate f is more than or equal to 0.2, the slope of the curve is larger, which indicates that the compound GH1 shows typical charge transfer luminescence characteristics in a high-polarity (f is more than or equal to 0.2) solvent. This indicates that the molecular excited state of the compound GH1 coexists with the local and charge transfer states, confirming that the local charge transfer hybrid state of the compound GH1 molecule with a twisted structure exhibits local luminescence characteristics at low polarity and CT-state luminescence characteristics at high polarity.
Example 2
Preparation of organic electroluminescent device
1) And (5) cleaning the ITO conductive glass. The ITO glass substrate is placed on a film developing frame and is ultrasonically cleaned by an ultrasonic device, and acetone, isopropanol, detergent, deionized water and isopropanol are sequentially used as cleaning solution, so that the aim of fully removing stains such as photoresist and the like possibly remaining on the surface of the ITO glass substrate and improving interface contact is fulfilled. Then drying in a vacuum oven;
2) Placing the ITO in an oxygen plasma etcher using an oxygen plasma (O) 2 Plasma) bombarding for twenty minutes to thoroughly remove possible residual organic matters on the surface of the ITO glass substrate;
3) PSS (Baytron P4083), a 40nm thick hole injection layer, spin-coated onto ITO, and then dried in a vacuum oven at 80 ℃ for 12 hours;
4) In a glove box in nitrogen atmosphere, a film with the thickness of 80nm is spin-coated on a PEDOT (PSS) layer to be used as a light-emitting layer of a non-doped device, and the device is named as A; spin-coating a thin film with the thickness of 60nm as a light emitting layer of a doping device, wherein the mass ratio of a host mCP to a green light micromolecule based on naphtho-dibenzothiophene is 95: 5. 93: 7. 90: 10. 85:15, corresponding electroluminescent devices are named as B1, B2, B3, B4; the mass ratio of the host mADN to the naphthothiodibenzofuran-based green small molecule was 95: 5. 93: 7. 90: 10. 85: and 15, corresponding electroluminescent devices are named as C1, C2, C3 and C4. And heating and annealing the luminescent layer at the temperature of 100 ℃ for 20 minutes to remove residual solvent and improve the appearance of the luminescent layer film.
5) In the vacuum evaporation chamber, the temperature is lower than 3 x 10 -4 Under the vacuum degree of Pa, a layer of 1,3,5-tri (1-phenyl-1H-benzimidazole-2-yl) benzene (TPBi) with the thickness of 20nm is evaporated on the organic film, and then a layer of cesium fluoride (CsF) with the thickness of 1.5nm is evaporated to be beneficial to electron injection. A 110nm thick aluminum cathode (Al) was then evaporated onto the CsF, where the cesium fluoride and aluminum layers were vacuum deposited through a shadow mask.
The effective area of the device is 0.16cm 2 . The thickness of the organic layer was measured with a quartz crystal monitoring thickness gauge. After the device is prepared, epoxy resin and thin-layer glass are used for polar curing in ultraviolet light and packaging. The device structure is (ITO/PEDOT: PSS/EMITTER (80/60 nm)/TPBi (20 nm)/CsF (1.5 nm)/Al (110 nm)).
The obtained electroluminescent devices were subjected to photoelectric property tests, and the test results are shown in table 1.
Table 1 electroluminescence performance data of the devices
As can be seen from Table 2, the maximum lumen efficiency of the undoped device prepared by using the electroluminescent material GH1 as the light-emitting layer is 8.2cd/A, the color coordinate is (0.24,0.50), and the ignition voltage is 3.0V. The current efficiency-current density graph is shown in fig. 4. When the current density is as high as 500mA/cm 2 In the process, the current efficiency of the device is still maintained at 7.3cd/A, and is attenuated by only 11%, so that the stable and high efficiency is maintained.
mCP is used as a doping parent, GH1 is used as a doping object, and when the doping content is 10wt%, the maximum lumen efficiency of the doping device is 18.6cd/A, the color coordinate is (0.25,0.51), and the starting voltage is 2.8V.
mADN is used as a doping parent, GH1 is used as a doping object, and when the doping content is 10wt%, the maximum lumen efficiency of the doping device is 20.3cd/A, the color coordinate is (0.26,0.52), and the starting voltage is 2.8V.
All devices show excellent photoelectric properties and have potential of practical application.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. A green light micromolecule based on naphtho-sulfur dibenzofuran is characterized in that the chemical structural formula is shown as formula I:
wherein R is methyl.
2. A method for preparing naphthodibenzothiophene-based small green light molecule according to claim 1, comprising the steps of:
(1) In an inert gas environment, completely dissolving 9-bromine-7,7-dimethyl-7H-benzo [ c ] fluorene compound 1 and compound 2 in a solvent, and reacting under the action of a catalyst and alkali to obtain compound 3;
(2) Under the inert gas environment, completely dissolving the compound 3 and the compound 4 in a solvent, and heating to react under the action of a catalyst, alkali and tetrabutylammonium bromide to obtain a compound 5;
(3) Dissolving a compound 5 in a solvent under an ice bath condition, then adding phosphorus pentoxide for reaction, adding the obtained reaction solution into ice water after the reaction, filtering to obtain filter residue, completely dissolving the filter residue in pyridine after the filter residue is dried in the air, and carrying out reflux reaction in an inert gas environment to obtain a compound 6;
(4) Dissolving the compound 6 in a solvent under an inert gas environment, and reacting under the action of an oxidant, namely hydrogen peroxide to obtain a compound 7;
(5) Dissolving a compound 8, a compound 9 and tetrabutylammonium bromide in a solvent under an inert gas environment, and performing a Suzuki coupling reaction under the action of a catalyst and alkali to obtain a compound 10;
(6) Under the inert gas environment, dissolving a compound 10, a compound 11 and tetrabutylammonium bromide in a solvent, and carrying out a Suzuki coupling reaction under the action of a catalyst and alkali to obtain a compound 12;
(7) Dissolving a compound 12, a compound 13 and tetrabutylammonium bromide in a solvent under an inert gas environment, and performing a Suzuki coupling reaction under the action of a catalyst and alkali to obtain a compound 14;
(8) Under the inert gas environment, completely dissolving a compound 14, a compound 7 and tetrabutylammonium bromide in a solvent, and performing a Suzuki coupling reaction under the action of a catalyst and alkali to obtain a final product compound 15;
the specific preparation route is shown as follows, wherein R is methyl:
3. the method for preparing naphthodibenzothiane-based green small molecule according to claim 2, wherein:
the solvent in the step (1) is at least one of 1,4-dioxane, toluene and N, N-dimethylformamide;
the catalyst in the step (1) is at least one of [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride and palladium acetate;
the alkali in the step (1) is at least one of potassium acetate, sodium acetate, potassium formate or sodium formate;
the reaction in the step (1) is carried out at 60-120 ℃ for 2-10h;
the solvent in the step (2) is at least one of toluene, xylene and tetrahydrofuran;
the catalyst in the step (2) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium;
the alkali in the step (2) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate;
the heating reaction in the step (2) is heating to 40-80 ℃ for 24-72h;
in the step (2), the molar ratio of the compound 3 to the compound 4 to the catalyst to the base to the tetrabutylammonium bromide is 1:1-3;
the ice bath condition in the step (3) is-20 to 10 ℃;
the solvent in the step (3) is at least one of trifluoromethanesulfonic acid and trifluoroacetic acid;
the molar ratio of the compound 5 to the phosphorus pentoxide in the step (3) is 1:5-10;
the time for adding the solvent and the phosphorus pentoxide to react in the step (3) is 4-12h; the reflux reaction in the inert gas environment in the step (3) refers to a reaction at 110 ℃ for 12 hours in the inert gas environment;
the solvent in the step (4) is at least one of acetic acid, formic acid and concentrated sulfuric acid; the mass fraction of the hydrogen peroxide in the step (4) is 20-50 wt%; the ratio of the molar weight of the compound 6 in the step (4) to the volume of hydrogen peroxide is 1mmol;
the reaction in the step (4) is carried out at room temperature for 12-36h;
the solvent in the step (5) is at least one of toluene, xylene and chlorobenzene; the catalyst in the step (5) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium; the alkali in the step (5) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate;
the reaction in the step (5) is carried out at 60-120 ℃ for 12-36h;
in the step (5), the molar ratio of the compound 8 to the compound 9 to the catalyst to the tetrabutylammonium bromide is 1:1-3;
the solvent in the step (6) is at least one of toluene, xylene and chlorobenzene; the catalyst in the step (6) is at least one of tetratriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium; the alkali in the step (6) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate;
the reaction in the step (6) is carried out at 60-120 ℃ for 12-36h;
in the step (6), the molar ratio of the compound 10, the compound 11, the catalyst, the alkali and the tetrabutylammonium bromide is 1:1-3;
the solvent in the step (7) is at least one of toluene, xylene and chlorobenzene; the catalyst in the step (7) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium; the alkali in the step (7) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate;
the reaction in the step (7) is carried out for 12-36h at 60-120 ℃;
in the step (7), the molar ratio of the compound 12, the compound 13, the catalyst, the alkali and the tetrabutylammonium bromide is 1:1-3;
the solvent in the step (8) is at least one of toluene, xylene and chlorobenzene; the catalyst in the step (8) is at least one of tetrakistriphenylphosphine palladium, palladium acetate and bis (dibenzylideneacetone) palladium; the alkali in the step (8) is at least one of potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate;
the reaction in the step (8) is carried out for 12-36h at 60-120 ℃;
in the step (8), the molar ratio of the compound 14, the compound 7, the catalyst, the base and the tetrabutylammonium bromide is 1:1-3.
4. The method for preparing naphthodibenzothiane-based green small molecule according to claim 2, wherein:
the solvent in the step (1) is 1,4-dioxane;
the catalyst in the step (1) is [1,1' -bis (diphenylphosphino) ferrocene ] palladium dichloride;
the alkali in the step (1) is potassium acetate;
the reaction in the step (1) is carried out at 90 ℃ for 6h;
in the step (1), the molar ratio of the compound 1, the compound 2, the catalyst and the base is 1;
the solvent in the step (2) is toluene;
the catalyst in the step (2) is tetratriphenylphosphine palladium;
the alkali in the step (2) is potassium carbonate;
the heating reaction in the step (2) is heating to 60 ℃ for 36 hours;
in step (2), the molar ratio of compound 3, compound 4, catalyst, base and tetrabutylammonium bromide is 1;
in the step (3), the ice bath condition is 0 ℃;
the solvent in the step (3) is trifluoroacetic acid;
the molar ratio of the compound 5 to the phosphorus pentoxide in the step (3) is 1:5;
the time for adding the solvent and the phosphorus pentoxide to react in the step (3) is 8h; the reflux reaction in the inert gas environment in the step (3) refers to a reaction at 110 ℃ for 12 hours in the inert gas environment;
the ratio of the molar weight of the compound 6 in the step (4) to the volume of the hydrogen peroxide solution is 1mmol;
the reaction in the step (4) is carried out at room temperature for 24 hours;
the solvent in the step (5) is toluene; the catalyst in the step (5) is tetratriphenylphosphine palladium; the alkali in the step (5) is potassium carbonate;
the reaction in the step (5) is carried out at 90 ℃ for 24 hours;
in step (5), the molar ratio of compound 8, compound 9, catalyst, base and tetrabutylammonium bromide is 1;
the solvent in the step (6) is toluene; the catalyst in the step (6) is tetratriphenylphosphine palladium; the alkali in the step (6) is potassium carbonate;
the reaction in the step (6) is carried out at 90 ℃ for 24 hours;
in step (6), the molar ratio of compound 10, compound 11, catalyst, base and tetrabutylammonium bromide is 1;
the solvent in the step (7) is toluene; the catalyst in the step (7) is tetratriphenylphosphine palladium; the alkali in the step (7) is potassium carbonate;
the reaction in the step (7) is carried out at 90 ℃ for 24 hours;
in step (7), the molar ratio of compound 12, compound 13, catalyst, base and tetrabutylammonium bromide is 1;
the solvent in the step (8) is toluene; the catalyst in the step (8) is tetratriphenylphosphine palladium; the alkali in the step (8) is potassium carbonate;
the reaction in the step (8) is carried out at 90 ℃ for 24h;
in step (8), the molar ratio of compound 14, compound 7, catalyst, base and tetrabutylammonium bromide is 1.
5. Use of the naphthodibenzothiaphene-based small green molecule as claimed in claim 1 as a light-emitting layer in the preparation of organic light-emitting diodes, organic field effect transistors, organic solar cells or organic laser diodes.
6. Use of the naphthodibenzothiane-based small green molecule of claim 5 for the preparation of a light-emitting layer of an organic light-emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode, characterized in that:
the green light micromolecules based on the naphtho-dibenzothiophene are independently used as a non-doped device luminescent layer material, or are used as a doped device luminescent layer material together with a doped parent, wherein the doped parent is mCP or mADN, and the mass percentage of the doped parent mCP or mADN in the luminescent layer material is 80-99%.
7. Use of the naphthodibenzothiane-based small green molecule of claim 6 for the preparation of a light-emitting layer of an organic light-emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode, wherein:
the luminescent layer is prepared by the following method: dissolving the green light micromolecules based on naphtho-dibenzothiophene by using an organic solvent, and preparing a light-emitting layer of a non-doped device by spin coating, ink-jet printing or printing film formation; or dissolving the doped matrix and the naphtho-dibenzothiophene-based green light micromolecule by using an organic solvent, and preparing the light emitting layer of the doped device by spin coating, ink-jet printing or printing film formation.
8. Use of the naphthodibenzothiane-based small green molecule of claim 7 for the preparation of a light-emitting layer of an organic light-emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode, characterized in that:
the organic solvent is at least one of tetrahydrofuran, chloroform, toluene, xylene and chlorobenzene.
9. Use of the naphthodibenzothiane-based small green molecule of claim 7 for the preparation of a light-emitting layer of an organic light-emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode, characterized in that:
the thickness of the luminescent layer is 10-1000 nm.
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| CN106699746A (en) * | 2017-01-04 | 2017-05-24 | 华南理工大学 | Bipolar small molecular light-emitting material based on naphthothiodibenzofuran unit as well as preparation method and application of bipolar small molecular light-emitting material |
| CN109837082A (en) * | 2017-11-24 | 2019-06-04 | 华南协同创新研究院 | A kind of electroluminescent material and the preparation method and application thereof |
| CN109929094A (en) * | 2018-12-31 | 2019-06-25 | 华南理工大学 | A kind of blue light frequency-doubling luminescent material and the preparation method and application thereof based on anthra sulphur dibenzofuran unit |
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| CN106699746A (en) * | 2017-01-04 | 2017-05-24 | 华南理工大学 | Bipolar small molecular light-emitting material based on naphthothiodibenzofuran unit as well as preparation method and application of bipolar small molecular light-emitting material |
| CN109837082A (en) * | 2017-11-24 | 2019-06-04 | 华南协同创新研究院 | A kind of electroluminescent material and the preparation method and application thereof |
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