CN109837082B - Electroluminescent material and preparation method and application thereof - Google Patents
Electroluminescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electroluminescent material, a preparation method and application thereof. The thiodibenzofuran acene unit is of a seven-element condensed ring structure, so that the injection and transmission of current carriers are facilitated due to good planarity, and the photoelectric property of the material is improved; the fused ring structure enables the thiohydrofluorene acene unit to have better rigidity, is beneficial to improving the heat resistance of the material, and meets the practical requirement of the material. The electroluminescent material based on the thionofluorenylacene unit obtained by Suzuki coupling reaction, Ullmann coupling reaction, still coupling reaction and the like has good solubility, can be dissolved by common organic solvents, and is prepared into a luminescent layer of a light-emitting diode by spin coating, ink-jet printing or printing film formation.
Description
Technical Field
The invention belongs to the technical field of organic photoelectricity, and particularly relates to an electroluminescent material, and a preparation method and application thereof.
Background
The electronic or optoelectronic industries such as organic/material light emitting diodes, organic field effect transistors, organic solar cells and the like are rapidly developed, wherein products based on Organic Light Emitting Diodes (OLED) are published for a long time, but because the current OLED device is prepared by adopting a vacuum evaporation process, instruments and equipment are expensive. The material utilization rate is low (20%), so that the price of an OLED product is high. The solution processing technology can make up the deficiency of vacuum evaporation and gradually attracts the attention of scientific research institutions and companies. The material has the advantages of good film forming property, mechanical processability and the like, and is suitable for solution processing, so that the development of a novel efficient and stable solution-processable material becomes a key.
The S, S-dioxo-dibenzo benzene unit is a blue light star unit with excellent performance and has higher fluorescence quantum yield; the sulfone group in the structure improves the electron affinity and the electron mobility of the molecule; the sulfur atom has better oxidation resistance and the like, and the polymer containing the 3, 7-substituted-S, S-dioxo-dibenzo-benzene unit shows excellent photoelectric properties. "Material Chemistry C" (Journal of Materials Chemistry C) reports that a single-layer device using a polymer in which a 3,7-S, S-dioxo-dibenzoylene unit is introduced into a polyfluorene main chain as a light-emitting layer has the maximum lumen efficiency as high as 7.1cd/A and the color coordinate is (0.16,0.18), and is the most efficient blue photopolymer at present. However, the S, S-dioxo-dibenzothiophene unit has strong electron-withdrawing ability, and the organic electroluminescent material containing the S, S-dioxo-dibenzothiophene unit can generate obvious intramolecular interaction, so that the spectrum is red-shifted, and the material with the expected color coordinate cannot be obtained. Therefore, it is necessary to research a novel blue light unit which has the advantages of S, S-dioxo-dibenzothiophene but has a slightly weak electron-withdrawing ability.
Disclosure of Invention
The primary object of the present invention is to provide an electroluminescent material for current organic/polymer light emitting diodes (O/PLEDs). The electroluminescent material has good solubility and excellent photoelectric property, is suitable for solution processing and ink-jet printing, and has great application potential.
The invention also aims to provide a preparation method of the electroluminescent material.
It is a further object of the present invention to provide applications of the electroluminescent material.
The purpose of the invention is realized by the following scheme:
an electroluminescent material, said material comprising the formula:
wherein, R is a group with hole or electron injection or transmission performance or a solubilizing group.
Preferably, R is an alkyl or alkoxy group having 1 to 2 carbon atoms, or a linear, branched or cyclic alkyl or alkoxy group having 3 to 20 carbon atoms, or an alkenyl group having 2 carbon atoms, or a linear, branched or cyclic alkenyl group having 3 to 20 carbon atoms, or an alkynyl group having 2 carbon atoms, or a linear, branched or cyclic alkynyl group having 3 to 20 carbon atoms, or a linear, branched or cyclic alkylcarbonyl group having 2 to 20 carbon atoms, or an aryl or heteroaryl group having 4 to 20 ring atoms, or an aralkyl or heteroarylalkyl group having 4 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 4 to 20 ring atoms, or an arylalkoxy or heteroarylalkoxy group having 4 to 20 ring atoms; or triphenylamine and derivatives thereof, carbazole and derivatives thereof, phenoxazine and derivatives thereof, phenothiazine and derivatives thereof, and acridine and derivatives thereof; or pyridine and its derivatives, oxadiazole and its derivatives, benzimidazole and its derivatives, triazole and its derivatives, triazine and its derivatives, quinoxaline and its derivatives.
Preferably, the structural unit Ar 1 To Ar 12 Is hydrogen or one of the following structural units:
wherein, the first and the second end of the pipe are connected with each other,
X＝O，S，Se，Te，N-R；
Y＝C，Si，Ge；
R 1 、R 2 、R 3 、R 4 is H, deuterium, F, alkenyl, alkynyl, nitrile group, amino group, nitro group, acyl group, alkoxy group, carbonyl group, sulfone group, aryl group, triphenylamine, carbazole, alkyl group having 1 to 30 carbon atoms, cycloalkyl group having 3 to 30 carbon atoms, aromatic hydrocarbon group having 6 to 60 carbon atoms or aromatic heterocyclic group having 3 to 60 carbon atoms.
The preparation method of the electroluminescent material comprises the following steps:
(1) o-bromobenzoic acid and ethanol are subjected to esterification reaction, and are dehydrated to obtain o-bromobenzoic acid ethyl ester, and then the o-bromobenzoic acid ethyl ester is completely dissolved in refined anhydrous tetrahydrofuran, and 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane is added in an inert gas environment to react at-78 ℃ to obtain ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate;
(2) under inert gas atmosphere, 3, 7-dibromo-S, S-dioxy dibenzothiophene and ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate are coupled through Suzuki to obtain a compound diethyl 2, 2' - (5, 5-dioxy diphenyl [ b, d ] thiophene-3, 7-yl) ethyl naphthoate;
(3) completely dissolving a compound diethyl 2, 2' - (5, 5-dioxy diphenyl [ b, d ] thiophene-3, 7-yl) ethyl naphthoate in refined anhydrous tetrahydrofuran, adding an alkyl form reagent under the condition of normal temperature, heating to 80 ℃, and reacting for 16h to obtain a compound 3, 7-bis (2- (2-dialkyl alcohol-2-yl) dibenzo [ b, d ] thiophene ]5, 5-dioxide;
(4) dissolving a compound 3, 7-bis (2- (2-dialkyl alcohol-2-yl) dibenzo [ b, d ] thiophene ]5, 5-dioxide in anhydrous dichloromethane, adding glacial acetic acid, reacting for 1h, and purifying to obtain a white solid 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide;
(5) dissolving a compound 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide in anhydrous trichloromethane, adding liquid bromine for bromination under a low temperature condition, and purifying to obtain white solid brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide;
(6) C-C coupling reaction or C-N coupling reaction
(i) C-C coupling reaction: under the inert gas environment, dissolving brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide in tetrahydrofuran, adding aryl boric acid ester or aryl boric acid, potassium carbonate aqueous solution and tetrakis (triphenylphosphine) palladium, carrying out Suzuki coupling reaction, and purifying to obtain the electroluminescent material based on the thiodibenzo-phenylene unit;
(ii) C-N coupling reaction: under the inert gas environment, bromide-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide is dissolved in a toluene solution, an arylamine monomer, sodium tert-butyl alkoxide, palladium acetate and tri-tert-butylphosphine are added to carry out C-N coupling reaction, and the electroluminescent material based on the thiooxyfluorenylacene unit is obtained after purification.
Preferably, in the synthesis step, the inert gas is argon; in the step (5), the low-temperature is-20 to 25 ℃, and the molar ratio of the 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide to the liquid bromine is 1:1 to 12.
Preferably, in the C-C coupling reaction in the step (6), the brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide, arylboronic acid ester or arylboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium are reacted at a molar ratio of 1: 2-6: 5-10: 0.02-0.1, and the C-C coupling reaction is carried out at a temperature of 50-120 ℃ for 8-48 hours.
Preferably, in the C-N coupling reaction of step (6), the brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide, the aromatic amine monomer, the sodium tert-butyl alkoxide, and the palladium acetate are in a molar ratio of 1:1 to 12:4.1 to 10:0.02 to 0.1, the palladium acetate and the tri-tert-butylphosphine are in a molar ratio of 1:1 to 4, the preferred palladium acetate and the tri-tert-butylphosphine are in a molar ratio of 1:2, and the C-N coupling reaction is carried out at 50 to 120 ℃ for 8 to 48 hours.
Use of an electroluminescent material for a light-emitting diode, a luminescent layer of a light-emitting diode, an organic field effect transistor, an organic solar cell or an organic laser diode.
Preferably, the method comprises the steps of dissolving the electroluminescent material with an organic solvent, and forming a film by spin coating, ink jet printing or printing, wherein the organic solvent is at least one of chlorobenzene, dichlorobenzene, toluene, xylene, tetrahydrofuran and chloroform.
Preferably, the structure of the light emitting diode device includes a stacked substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer in this order, or includes a stacked substrate, a cathode layer, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode layer in this order.
Compared with the prior art, the invention has the following advantages:
(1) the thionofluorenylacene unit related by the invention has the advantages that the introduction of the weak-polarity phenyl group enables the D-A function in the molecule of the thionofluorenylacene new unit to be weaker, the charge transfer function in the molecule is weakened, the red shift of the spectrum is avoided, and the thionofluorenylacene unit is still a blue light unit.
(2) Compared with a single S, S-dioxo-dibenzobenzene unit, the fused ring structure of the thionofluorenylacene unit has a coplanar rigid structure, more modifiable sites, and the introduction of solubilizing groups can obviously improve the solubility of a new unit, so that the molecular structure is more stable and the thermal stability is better. It is obvious from the structure that the thiobenzofluorene unit has four alkyl chains, and a single S, S-dioxo-dibenzothiophene has only two alkyl chains at most, and the solubility of the S, S-dioxo-dibenzothiophene is certainly good. The thiodibenzoacene is a multi-element condensed ring structure, has coplanarity, alternate single bond and double bond, is a stable structure, has better rigidity than single S, S-dioxo-dibenzothiophene, and has direct proportion relation between thermal stability and rigidity.
(3) According to the electroluminescent material based on the thiooxyfluorene acene, due to the seven-element fused ring structure of the thiooxyfluorene acene unit, a plurality of modified active sites are provided, the chemical modification is stronger, a long alkyl chain can be introduced to improve the solubility of the material, the material has better solubility, and the luminescent layer based on the material does not need annealing treatment when an electroluminescent device is prepared, so that the preparation process is simpler.
(4) The novel fused ring structure-thiodibenzothiophene unit synthesized by the method has the advantages of an S, S-dioxo-dibenzothiophene unit, and simultaneously, the plane structure is increased, so that the electronic transmission performance of the material is favorably improved.
(5) The electroluminescent material based on the thionofluorene acene unit has good solubility, is suitable for solution processing, has good fluorescence quantum yield, is beneficial to obtaining high-efficiency and stable blue light device performance of a light-emitting device, can simultaneously improve the light-emitting efficiency and the service life of the device, and can meet the requirement of full-color display. Therefore, the organic light-emitting diode has great development potential and prospect in the field of organic electronic display.
Drawings
FIG. 1 differential scanning calorimetry curves for compounds B1-B4.
Fig. 2 shows the ultraviolet-visible absorption spectrum of compound B1 in the thin film state.
FIG. 3 fluorescence spectrum of Compound B1 in thin film state.
Detailed Description
The present invention will be further described with reference to the following examples.
EXAMPLE 12 preparation of ethyl bromobenzoate
In a 500mL three-necked flask, 2-bromobenzoic acid (20.1g, 0.1mol) was dissolved in 200mL of ethanol, and 20mL of concentrated sulfuric acid was added dropwise to the reaction mixture, and after stirring at room temperature for 12 hours, the reaction was stopped, the reaction was quenched with water, extracted with dichloromethane and dried over anhydrous magnesium sulfate, and the solution was concentrated to give a yellow liquid, which was purified by silica gel column chromatography with a mixed solvent of petroleum ether and dichloromethane (7/1, v/v) as an eluent in a yield of 84%. 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:
example 2 preparation of ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate
Under the protection of inert gas, ethyl 2-bromobenzoate (17.5g, 76.4mmol) was dissolved in 250ml of anhydrous tetrahydrofuran, and a solution of n-hexane (38.2ml, 91.7mmol) of n-butyllithium at a concentration of 2.4mol/L was slowly added dropwise thereto, and after stirring at ordinary temperature for 1 hour, 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane (25.6g, 0.14mol) was added to the reaction system, the reaction was stopped, quenched with water, extracted with dichloromethane and dried over anhydrous magnesium sulfate, the solution was concentrated to give a yellowish liquid, purified by silica gel column chromatography, and a mixed solvent of petroleum ether/dichloromethane (5/1, v/v) was used as an eluent to give a white solid in a yield of 87%. 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:
EXAMPLE 3 preparation of diethyl 2, 2' - (5, 5-dioxodiphenyl [ b, d ] phenyl-3, 7-yl) di (benzene-3-carboxylate)
Ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate (8.4g, 30.4mmol), 2, 7-dibromo-S, S-dioxadibenzobenzene (20.0g, 45.6mmol), tetrabutylammonium bromide (0.49g, 1.52mmol), palladium (1.76g, 1.52mmol) triphenylphosphine dichloride as a catalyst, and 200mL toluene were added to a 500mL three-necked flask under an argon atmosphere, heated with stirring, and when the temperature stabilized at 110 ℃, an organic base (20mL) and K were added 2 CO 3 42mL of an aqueous solution (41.95g, 0.30mol) was reacted for 12 h. The reaction solution was concentrated and purified by silica gel column chromatography using a mixed solvent of petroleum ether and methylene chloride (3/1, v/v) as an eluent, to give a pale yellow solid with a yield of 75%. 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:
example 43 preparation of 7, 7-bis (2- (2-dipropanol-2-yl) dibenzo [ b, d ] thiophene ]5, 5-dioxide
Under the protection of inert gas, diethyl 2, 2' - (5, 5-dioxy diphenyl [ b, d)]Phenyl-3, 7-yl) bis (benzene-3-carboxylate) (7.2g, 14mmol) was dissolved in 80ml of purified anhydrous THF and 1.0mol L of THF was added dropwise -1 Octyl magnesium bromide (70ml, 70mmol), heating to 80 deg.C, refluxing, and reacting for 16 h. After cooling to room temperature, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was completely washed with brine and dried over anhydrous magnesium sulfate. After the solution was concentrated, the next reaction was carried out directly.
Example 512, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide preparation
Mixing 3, 7-di (2- (2-dipropanol-2-yl) dibenzo [ b, d]Thiophene(s)]5, 5-dioxide (3.2g, 6.6mmol) was dissolved in 80mL of glacial acetic acid and reacted for 1 h. After the solution is concentrated, the solution is purified by silica gel column chromatography, and a mixed solvent (8/1, v/v) of petroleum ether and dichloromethane is used as an eluent. The crude product was recrystallized from ethanol to give white crystals with a yield of 80%. 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:
example preparation of 62, 10-dibromo-12, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide
Mixing 12,12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ]]Thiophene 6, 6-dioxide (2.5g, 5.6mmol) was dissolved in 10ml of carbon tetrachloride, liquid bromine (1.0g, 6.2mmol) was added under ice bath conditions, after 24 hours of reaction, the reaction was quenched with saturated sodium bisulfite and extracted with ethyl acetate, after drying over anhydrous magnesium sulfate, purification was performed by silica gel column chromatography, and a mixed solvent of petroleum ether and dichloromethane (8/1, v/v) was used as an eluent to obtain a white solid. Yield: 86 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:
EXAMPLE 7 Synthesis of Compound B1
2, 10-dibromo-12, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] was added to a 100mL three-necked flask under an argon atmosphere]Thiophene 6, 6-dioxide (1.44g, 2.4mol), diphenylamine (0.85g, 5.0mmol), sodium tert-butoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml of toluene. The mixture was stirred while heating to 85 ℃ and 0.12ml of a toluene solution of tri-t-butylphosphine (concentration: 2.0mol/L) was added to the mixture to conduct a reaction for 12 hours. After the reaction is stopped, the solvent is concentrated, the crude product is purified by column chromatography, and a mixed solvent (4/1, v/v) of petroleum ether and dichloromethane is used as an eluent, so that emerald green solid is finally obtained. 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 Differential Scanning Calorimetry (DSC) curve of compound B1 is shown in figure 1. As can be seen from the figure, compound B1 has no melting peak and crystallization peak during the whole heating process, and only has a glass transition peak, which indicates that compound B1 can form an amorphous state under solid conditions, and is not easy to crystallize when preparing a light-emitting layer of an organic light-emitting diode, which is beneficial to normal use of the device. From the DSC curve, it was found that the glass transition temperature of compound B1 was 90 ℃ in this order.
The ultraviolet-visible absorption spectrum of the compound B1 in the thin film state is shown in fig. 2, and it is understood from fig. 2 that the maximum absorption peak of B1 in the thin film state is 382nm, and the absorption is attributed to the conjugated main chain of the compound B1. Maximum absorption edge (. lamda.) of Compound B1 in thin film form max ) 430nm, according to an empirical formula, the optical band gap E of the compound g ＝1240/λ max 1240/430eV is 2.88eV, with a wider band gap.
The fluorescence emission spectrum of compound B1 in the thin film state is shown in fig. 3, and it can be seen from fig. 3 that the maximum emission peak of B1 in the thin film state is 470nm, which realizes blue light emission, the half-peak width is narrower, and 59nm, which can realize blue light emission with better color purity in the device.
EXAMPLE 8 Synthesis of Compound B2
2, 10-dibromo-12, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] was added to a 100mL three-necked flask under an argon atmosphere]Thiophene 6, 6-dioxide (1.44g, 2.4mol), carbazole (0.84g, 5.0mmol), sodium tert-butoxide (1.84g, 19.2mmol), palladium acetate (27mg, 0.12mmol) and 50ml toluene. The mixture was stirred while heating to 85 ℃ and 0.12ml of a toluene solution of tri-t-butylphosphine (concentration: 2.0mol/L) was added thereto to conduct a reaction for 12 hours. After the reaction is stopped, the solvent is concentrated, the crude product is purified by column chromatography, and a mixed solvent of petroleum ether and dichloromethane (4/1, v/v) is used as eluent, so that off-white solid is finally obtained. 1 H NMR、 13 C NMR, 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:
the Differential Scanning Calorimetry (DSC) curve of compound B2 is shown in figure 1. As can be seen, compound B2 showed no melting and crystallization peaks throughout the heating process, but only a glass transition peak, indicating that compound B2 was able to form an amorphous state under solid state conditions. From the DSC curves, the glass transition temperatures of the compounds B1 to B4 were found to be 92 ℃ in this order.
EXAMPLE 9 Synthesis of Compound B3
2, 10-dibromo-12, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] was added to a 100mL three-necked flask under an argon atmosphere]Thiophene 6, 6-dioxide (1.44g, 2.4mol), benzimidazole boronic acid (1.57g, 5.0mmol), aqueous potassium carbonate (2mol/L, 2.65g/9.6ml deionized water, 19.2mmol), palladium tetrakistriphenylphosphine (139mg, 0.12mmol) and 50ml tetrahydrofuran. The mixture is heated and stirred to 85 ℃ and reacts for 12 hours. After the reaction is stopped, the solvent is concentrated, the crude product is purified by column chromatography, and a mixed solvent (3/1, v/v) of petroleum ether and dichloromethane is used as an eluent, so that an off-white solid is finally obtained. 1 H NMR、 13 The CNMR, MS and element analysis result show that the obtained compound is a target productThe chemical reaction equation of the preparation process is shown as follows:
the Differential Scanning Calorimetry (DSC) curve of compound B3 is shown in figure 1. As can be seen from the figure, compound B3 shows no melting peak and no crystallization peak, and only shows a glass transition peak during the whole heating process, which indicates that compound B3 can form an amorphous state under solid state conditions. From the DSC curve, the glass transition temperature of Compound B3 was found to be 96 ℃.
EXAMPLE 10 Synthesis of Compound B4
2, 10-dibromo-12, 12,15, 15-tetramethyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] was added to a 100mL three-necked flask under an argon atmosphere]Thiophene 6, 6-dioxide (1.44g, 2.4mol), 9-dimethyl-2-fluorenylboronic acid (1.19g, 5.0mmol), aqueous potassium carbonate (2mol/L, 2.65g/9.6ml deionized water, 19.2mmol), palladium tetrakistriphenylphosphine (139mg, 0.12mmol) and 50ml tetrahydrofuran. Heating and stirring to 85 ℃, and reacting for 12 h. After the reaction is stopped, the solvent is concentrated, the crude product is purified by column chromatography, and a mixed solvent (4/1, v/v) of petroleum ether and dichloromethane is used as an eluent, so that a emerald green solid is finally obtained. 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:
the Differential Scanning Calorimetry (DSC) curve of compound B4 is shown in figure 1. As can be seen from the figure, compound B4 shows no melting peak and no crystallization peak during the whole heating process, and only shows a glass transition peak, which indicates that compound B4 can form an amorphous state under solid state conditions, and is not easy to crystallize when preparing the light-emitting layer of an organic light-emitting diode, which is beneficial to normal use of the device. From the DSC curve, the glass transition temperature of Compound B4 was found to be 94 ℃.
EXAMPLE 11 Synthesis of Compound B5
In a 100mL three-necked flask, under an argon atmosphere, 3, 7-dibromo-S, S-dioxodibenzothiophene (0.90g, 2.4mol), 9-dimethyl-2-fluorenylboronic acid (1.19g, 5.0mmol), an aqueous solution of potassium carbonate (2mol/L, 2.65g/9.6mL deionized water, 19.2mmol), tetrakistriphenylphosphine palladium (139mg, 0.12mmol), and 40mL tetrahydrofuran were added. The mixture is heated and stirred to 75 ℃ and reacts for 12 h. After the reaction is stopped, the solvent is concentrated, the crude product is purified by column chromatography, and a mixed solvent (4/1, v/v) of petroleum ether and dichloromethane is used as an eluent, so that emerald green solid is finally obtained. 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:
example 12
Preparation of organic electroluminescent device
1) And (4) 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, was 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 layer of luminescent organic film with the thickness of 80nm is coated on a PEDOT (PolyEthylenediamine) PSS layer in a spinning way, and then the mixture is heated and annealed for 20 minutes on a heating table at the temperature of 80 ℃ so as 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 A layer of cesium fluoride (CsF) with the thickness of 1.5nm is evaporated on the organic film under the vacuum degree of Pa, so that electron injection is facilitated. 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 single-layer device structure is (ITO/PEDOT: PSS/EMITTER (80nm)/CsF (1.5nm)/Al (110 nm)).
The obtained electroluminescent devices were subjected to photoelectric property tests, and the test results are shown in table 1.
Electroluminescent Properties data for the compounds of Table 1
The compounds B1-B5 are used as light-emitting layers to prepare ITO/PEDOT PSS/EMITTER/CsF/Al single-layer devices, and the maximum lumen efficiencies are 4.09cd/A, 3.50cd/A, 2.78cd/A, 3.96cd/A and 0.65cd/A respectively. Wherein the maximum brightness of the device based on the compound B1 can reach 24889cd/m 2 . The compounds B1-B4 showed better photoelectric properties and all achieved blue light emission with better color purity.
Comparative compounds B4 and B5, structurally, differ in that the core is different: compound B4 is a thiofluorenylacene unit bonded to a fluorene unit; compound B5 is a single S, S-dioxo-dibenzo-benzene unit bonded to a fluorene unit. Under the same device structure, the electroluminescent properties of the two materials are obviously different. As can be seen from the data in Table 1, the maximum lumen efficiency of the device based on Compound B5 was only 1.25cd/A, and the maximum luminance was 3957cd/m 2 (ii) a The maximum lumen efficiency of the device based on the compound B4 is 3.96cd/A, which is improved by two times compared with the former performance; maximum luminance is 10252cd/m 2 The photoelectric property of the material is obviously improved by 2.6 times of that of the former. Since the conjugation degree of the compound B4 is greater than that of the compound B5, the spectrum is red-shifted, and the color coordinate is increased from (0.16,0.10) to (0.14,0.16), but the compound B4 still has the color coordinateIn the deep blue region. (deep blue region (x + y. ltoreq.0.3)). By comparison, the electroluminescent materials based on the thiodibenzofuran acene unit are excellent in performance and have application potential.
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 that do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are intended to be included in the scope of the present invention.
Claims (8)
1. An electroluminescent material, comprising one of the following structural formulas:
2. a method of preparing an electroluminescent material as claimed in claim 1, characterized in that it comprises the steps of:
(1) o-bromobenzoic acid and ethanol are subjected to esterification reaction, and are dehydrated to obtain o-bromobenzoic acid ethyl ester, and then the o-bromobenzoic acid ethyl ester is completely dissolved in refined anhydrous tetrahydrofuran, and 2-isopropoxy-4, 4,5, 5-tetramethyl-1, 3, 2-dioxaborane is added in an inert gas environment to react at-78 ℃ to obtain ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate;
(2) under inert gas atmosphere, 3, 7-dibromo-S, S-dioxydibenzothiophene is coupled with ethyl 2- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane-2-yl) benzoate by Suzuki to obtain a compound diethyl 2, 2' - (5, 5-dioxy diphenyl [ b, d ] thiophene-3, 7-yl) ethyl naphthoate;
(3) completely dissolving a compound diethyl 2, 2' - (5, 5-dioxy diphenyl [ b, d ] thiophene-3, 7-yl) ethyl naphthoate in refined anhydrous tetrahydrofuran, adding an alkyl form reagent under the condition of normal temperature, heating to 80 ℃, and reacting for 16h to obtain a compound 3, 7-bis (2- (2-dialkyl alcohol-2-yl) dibenzo [ b, d ] thiophene ]5, 5-dioxide;
(4) dissolving a compound 3, 7-bis (2- (2-dialkyl alcohol-2-yl) dibenzo [ b, d ] thiophene ]5, 5-dioxide in anhydrous dichloromethane, adding glacial acetic acid, reacting for 1h, and purifying to obtain a white solid 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide;
(5) dissolving a compound 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide in anhydrous trichloromethane, adding liquid bromine for bromination under a low temperature condition, and purifying to obtain white solid brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide;
(6) C-C coupling reaction or C-N coupling reaction
(i) C-C coupling reaction: dissolving bromide-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide in tetrahydrofuran under an inert gas environment, adding aryl boric acid or aryl boric acid, potassium carbonate aqueous solution and tetrakis (triphenylphosphine) palladium, carrying out Suzuki coupling reaction, and purifying to obtain the electroluminescent material based on the thiodibenzo-phenylene unit;
(ii) C-N coupling reaction: under the inert gas environment, bromide-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide is dissolved in a toluene solution, an arylamine monomer, sodium tert-butyl alkoxide, palladium acetate and tri-tert-butylphosphine are added to carry out C-N coupling reaction, and the electroluminescent material based on the thiooxyfluorenylacene unit is obtained after purification.
3. The method of claim 2, wherein in the step of synthesizing, the inert gas is argon; in the step (5), the low-temperature is-20 to 25 ℃, and the molar ratio of the 12,12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide to liquid bromine is 1:1 to 12.
4. The method according to claim 2, wherein in the C-C coupling reaction in step (6), the mole ratio of the brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide, arylboronic acid ester or arylboronic acid, potassium carbonate and tetrakis (triphenylphosphine) palladium is 1:2 to 6:5 to 10:0.02 to 0.1, and the C-C coupling reaction is carried out at 50 to 120 ℃ for 8 to 48 hours.
5. The method according to claim 2, wherein in the C-N coupling reaction in the step (6), the mole ratio of the brominated-12, 12,15, 15-tetraalkyl-12, 15-dihydrodibenzo [3,2-b:2 '3' -d ] thiophene 6, 6-dioxide to the arylamine monomer to the sodium tert-butyl alkoxide to the palladium acetate is 1:1 to 12:4.1 to 10:0.02 to 0.1; the molar ratio of the palladium acetate to the tri-tert-butylphosphine is 1: 1-4, the molar ratio of the palladium acetate to the tri-tert-butylphosphine is 1:2, and the C-N coupling reaction is carried out at 50-120 ℃ for 8-48 hours.
6. Use of an electroluminescent material as claimed in claim 1, characterized in that: the electroluminescent material is used for light-emitting diodes, light-emitting layers of the light-emitting diodes, organic field effect transistors, organic solar cells or organic laser diodes.
7. The use according to claim 6, comprising the step of dissolving the electroluminescent material in an organic solvent, and forming a film by spin coating, ink jet printing or printing, wherein the organic solvent is at least one of chlorobenzene, dichlorobenzene, toluene, xylene, tetrahydrofuran and chloroform.
8. The use according to claim 6, wherein the structure of the light emitting diode device comprises, in order, a stacked substrate, an anode layer, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode layer, or comprises, in order, a stacked substrate, a cathode layer, an electron injection layer, an electron transport layer, a light emitting layer, a hole transport layer, a hole injection layer, and an anode layer.
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