CN112321585B - Asymmetric substituted diphenyl pyridine compound and preparation and application thereof - Google Patents
Asymmetric substituted diphenyl pyridine compound and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to an organic small molecule photoelectric functionThe technical field of energy materials, and discloses an asymmetrically substituted diphenylpyridine compound, and a preparation method and an application thereof. The unsymmetrically substituted diphenyl pyridine compound is more than one of a formula I or a formula II. The invention also discloses a preparation method of the unsymmetrically substituted diphenylpyridine compound. The asymmetrically substituted diphenylpyridine compound is used for preparing an organic electron transport material. The organic electron transport material comprises more than one of the unsymmetrically substituted diphenyl pyridine compounds. The asymmetrically substituted diphenylpyridine compound has high decomposition temperature and glass transition temperature, is suitable for high-stability devices, is easy to remove bromine-containing raw materials and intermediates, and is beneficial to long-term stable operation of OLEDs. The compound of the invention can be used as an organic electron transport material to improve the efficiency of a photoelectric device. The compound provided by the invention is used as an organic micromolecular electron transport material to be applied to photoelectric devices.
Description
Technical Field
The invention belongs to the technical field of organic micromolecule photoelectric functional materials, relates to an electron transport material, and particularly relates to an asymmetrically substituted diphenylpyridine compound, and preparation and application thereof. The asymmetrically substituted diphenylpyridine compound is used as an electron transport material, has high thermal decomposition temperature and glass transition temperature, and is applied to an electron transport layer of photoelectric devices such as high-performance organic light-emitting diodes.
Background
Organic Light Emitting Diodes (OLEDs) are composed of electrodes, charge transport layers, and light emitting layers. Generally, the hole mobility of organic hole transport materials is higher than the electron mobility of organic Electron Transport Materials (ETMs), and applying them to OLED devices causes carrier imbalance of the devices, which is not favorable for improving efficiency and stability of the devices. Therefore, the design and preparation of the intrinsic-state or doped-state high-mobility organic molecular electron transport material have extremely important significance for reducing the working voltage of the OLED, improving the electroluminescent efficiency and improving the device stability. However, in order to enhance electron mobility, enhanced conjugation or intermolecular forces of the ETMs are often enhanced, which may cause the organic electron transport material to have reduced solubility, making purification difficult; meanwhile, trace residual halogenated impurities derived from reaction raw materials, intermediates or byproducts can greatly harm the stability of the OLED.
In addition, the glass transition temperature and the electron mobility also have a trade-off relationship, and the improvement of the mobility generally needs to enhance the conjugation or intermolecular force, so that the material is easy to crystallize, the glass transition temperature is influenced, and the practical application in the field of OLED devices is not facilitated.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a class of unsymmetrically substituted diphenylpyridine compounds and a preparation method thereof. The asymmetric substituted diphenylpyridine compound is easy to synthesize and purify, can promote the removal of halogen impurities, and has high decomposition temperature and glass transition temperature. The asymmetrically substituted diphenylpyridine derivatives of the present invention are useful as organic electron transport materials.
The invention also aims to provide application of the unsymmetrically substituted diphenylpyridine compound. The asymmetrically substituted diphenylpyridine derivative is used as an organic electron transport material and applied to photoelectric devices such as organic light-emitting diodes.
The purpose of the invention is realized by the following technical scheme:
an asymmetrically substituted diphenylpyridine compound, which has a structural formula I or II:
the preparation method of the asymmetric substituted diphenylpyridine compound with high decomposition temperature and high glass transition temperature comprises the following steps:
(1) under the condition of protective gas, 2, 6-dihalogen pyridine and 3-halophenylboronic acid react in an organic solvent under the action of a catalytic system, and the dihalogen diphenyl pyridine compound is obtained after subsequent treatment;
the structure of the dihalodiphenylpyridine compoundComprises the following steps:
(2) reacting the dihalogenated diphenylpyridine compound obtained in the step (1) with diamyl diboron, and carrying out subsequent treatment to obtain an intermediate product containing boric acid ester;
the intermediate product containing borate has the structure:
(3) carrying out Suzuki coupling reaction on the intermediate product containing the borate obtained in the step (2) and a triazine compound (2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-bis ((1,1' -biphenyl) -4-yl) -6-chloro-1, 3, 5-triazine), and carrying out subsequent treatment to obtain a triazine-containing intermediate product;
the 2-chloro-4, 6-diphenyl-1, 3, 5-triazine has a structure
The structure of the 2, 4-bis ((1,1' -biphenyl) -4-yl) -6-chloro-1, 3, 5-triazine is
The triazine-containing intermediate product has the structure
(4) In a catalytic system, performing Suzuki coupling reaction on the triazine-containing intermediate product obtained in the step (3) and 3-bromo-1, 10-phenanthroline, and performing subsequent treatment to obtain an electron transport material Phen-2PhPy-TRZ (formula I) or Phen-Py-BPTRZ (formula II) containing pyridine, phenanthroline and triazine groups.
The 2, 6-dihalopyridine in the step (1) is 2, 6-dibromopyridine, 2, 6-dichloropyridine or 2, 6-diiodopyridine, and preferably 2, 6-dibromopyridine; the 3-halogen phenylboronic acid is 3-bromobenzene boric acid, 3-chlorobenzene boric acid or 3-iodophenylboronic acid, and 3-bromobenzene boric acid is preferred.
The reaction temperature in the step (1) is 80-82 ℃, and the reaction time is 10-15 h, preferably 12 h.
The organic solvent in the step (1) is more than one of toluene, tetrahydrofuran, dioxane and DMSO, and toluene is preferred; the catalytic system comprises a palladium catalyst, preferably tetrakis (triphenylphosphine) palladium; the catalytic system further comprises a phase transfer agent, preferably ethanol, and a basic compound, preferably potassium carbonate. The molar ratio of the 2, 6-dihalopyridine to the 3-halophenylboronic acid to the tetrakis (triphenylphosphine) palladium is 1: (2-2.1): (0.01 to 0.06);
the reaction temperature in the step (2) is 80-85 ℃, the reaction time is 8-12 h, and preferably 10 h; the reaction is carried out under the action of a catalytic system, wherein the catalytic system comprises a palladium catalyst, and the palladium catalyst is bis (triphenylphosphine) palladium dichloride; the molar ratio of the dihalogenated diphenylpyridine compound to the bis (triphenylphosphine) palladium dichloride and the bis (valeryl diboron) is 1: (2.2-2.4): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium; the organic solvent is more than one of DMF, DMSO and tetrahydrofuran, and tetrahydrofuran is preferred; the catalytic system also comprises a basic compound, preferably potassium acetate.
The reaction temperature in the step (3) is 80-90 ℃, and the reaction time is 10-12 h; the reaction is carried out in a catalytic system, wherein the catalytic system comprises a palladium catalyst, and the palladium catalyst is tetrakis (triphenylphosphine) palladium; the molar ratio of the intermediate product containing borate ester, the triazine compound (2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-bis ((1,1' -biphenyl) -4-yl) -6-chloro-1, 3, 5-triazine), and the palladium catalyst is 1: (1.1-1.3): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium, and the organic solvent is more than one of toluene, tetrahydrofuran, dioxane and DMSO; the organic solvent is preferably toluene; the reaction system also comprises a phase transfer agent and an alkaline aqueous solution, wherein the phase transfer agent is ethanol, and the alkaline aqueous solution is preferably a sodium carbonate aqueous solution.
The reaction temperature in the step (4) is 85-95 ℃, and the reaction time is 10-15 h, preferably 12 h. (ii) a The catalytic system comprises a palladium catalyst, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium; the molar ratio of the triazine-containing intermediate product to the 1, 10-phenanthroline and palladium catalyst is 1: (1.1-1.2): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium, and the organic solvent is more than one of toluene, tetrahydrofuran, dioxane and DMSO; the organic solvent is preferably toluene; the reaction system also comprises a phase transfer agent and an alkaline aqueous solution, wherein the phase transfer agent is ethanol, and the alkaline aqueous solution is preferably potassium carbonate aqueous solution.
The subsequent treatment in the step (1) is reaction completion, cooling, reduced pressure distillation, water and dichloromethane are added to extract a water layer, and an organic layer is dried by anhydrous magnesium sulfate, filtered, reduced pressure distillation and then purified by column chromatography.
The subsequent treatment in the step (2) is to remove tetrahydrofuran by reduced pressure distillation after the reaction is finished, add water and dichloromethane for extraction, use anhydrous magnesium sulfate to dry, filter and reduce pressure distillation the organic layer, and then purify the product by column chromatography separation and recrystallization;
the subsequent treatment in the step (3) is to remove the solvent by reduced pressure distillation after the reaction is finished, then add distilled water and dichloromethane to extract the water layer, dry and filter the organic layer by using anhydrous magnesium sulfate, and purify the product by solvent washing, recrystallization and column chromatography separation and purification methods;
and (4) the subsequent treatment refers to cooling to room temperature after the reaction is finished, distilling under reduced pressure to remove the solvent, adding water and dichloromethane to extract a water layer, drying an organic layer by anhydrous magnesium sulfate, filtering, distilling under reduced pressure to remove dichloromethane, and purifying the product by recrystallization, column chromatography separation and solvent washing methods.
The organic electron transport material is an asymmetric substituted diphenylpyridine compound, preferably more than one of the asymmetric substituted diphenylpyridine compounds Phen-2PhPy-TRZ (formula I) or Phen-Py-BPTRZ (formula II) with high thermal decomposition temperature and glass transition temperature.
A doped organic electron transport material comprises the organic electron transport material and a dopant, wherein the dopant is an 8-hydroxyquinoline lithium complex.
The mass ratio of the organic electron transport material to the dopant is 1: (0.3-2).
The organic micromolecule electron transport material or the doped organic electron transport material is used for preparing photoelectric devices, particularly organic electroluminescent devices, and is used as an electron transport layer of the organic electroluminescent devices. The light emitting device is a light emitting diode. The light emitting device is preferably a phosphorescent device.
The principle of the invention is as follows:
the invention introduces 1, 10-phenanthroline group into two ends of 2, 6-diphenylpyridine compound by asymmetric substitution
And 2,4, 6-triphenyl-1, 3, 5-triazine
Or 2, 4-bis ([1,1' -biphenyl)]-4-yl) -6-phenyl-1, 3, 5-triazine
A group. The source of the raw material 2, 6-bis (3-bromophenyl) pyridine is easy to obtain, and the distorted molecular structure is favorable for improving the solubility and purifying materials and forming an amorphous state. The pyridine, the 1, 10-phenanthroline and the triazine units which are electron-deficient can reduce the LUMO energy level and improve the electron injection and transmission characteristics. In general, the molecular design can simultaneously improve the thermal stability and the glass transition temperature of the material and expand the application potential of the material.
The invention has the following advantages and beneficial effects:
(1) the asymmetrically substituted diphenylpyridine compound has the advantages of simple structure and preparation, easy purification, less synthesis steps and capability of effectively improving the electron injection and transmission capability of materials, and is bridged by a dibromo diphenylpyridine compound, namely Phen-2PhPy-TRZ (formula I) or Phen-Py-BPTRZ (formula II) with 1, 10-phenanthroline and triazine groups.
(2) The asymmetrically substituted diphenylpyridine compound is obtained by four-step synthesis, wherein the bromine-containing intermediate comprises a first-step dibromo diphenylpyridine compound and a fourth-step raw material of 3-bromo-1, 10 phenanthroline, and the solubility and polarity of the two bromine-containing intermediates are greatly different from those of Phen-2PhPy-TRZ (formula I) or Phen-Py-BPTRZ (formula II), so that the two bromine-containing intermediates are easy to remove, and the influence of halogen impurities on the stability of an OLED is greatly eliminated.
(3) The asymmetric substituted diphenylpyridine derivative Phen-2PhPy-TRZ (formula I) or Phen-Py-BPTRZ (formula II) has high thermal decomposition temperature and glass transition temperature. Wherein the decomposition temperature of the compound Phen-2PhPy-TRZ corresponds to 416 ℃ (i.e. 1% weight loss corresponds to the temperature), 5% weight loss corresponds to the temperature of 448.7 ℃, and the glass transition of the material occurs in the processes of the first round of temperature reduction and the second round of temperature reduction, and corresponds to about 129.3 ℃. The material has high decomposition temperature and glass transition temperature, corresponds to high thermal stability and film shape stability, and provides possibility for further improving the stability of devices.
(4) The asymmetrically substituted diphenylpyridine derivative can be used as an electron transport material to dope Liq and then applied to a red light phosphorescence device, so that the device has high efficiency. At 1000cd m-2The working voltage of the compound Phen-2PhPy-TRZ device is only 4V, while the current efficiency and the power efficiency respectively reach 13.4cd/A and 10.6lm/W, which belong to the front row in the same red phosphorescence device.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ of example 1;
FIG. 2 is a thermal stability curve of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ of example 1; wherein (a) and (b) are a thermogravimetric loss curve and a differential scanning calorimetry curve of the organic electron transport material Phen-2PhPy-TRZ of example 1, respectively;
FIG. 3 is a UV-VIS absorption spectrum of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ of example 1;
FIG. 4 is a current density-voltage-luminance curve of a red phosphorescent organic electroluminescent device of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ of example 1;
FIG. 5 is a graph of luminous efficiency vs. luminance for a red phosphorescent organic electroluminescent device of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ of example 1;
FIG. 6 is a power efficiency-luminance curve of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ red phosphorescent organic electroluminescent device of example 1.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
An asymmetric substituted diphenylpyridine compound electron transport material Phen-2PhPy-TRZ with high decomposition temperature and high glass transition temperature has the structure:
the synthesis procedure for the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ described in this example was as follows:
the method comprises the following steps: preparation of 2, 6-bis (3-bromophenyl) pyridine (1)
In N2Under the atmosphere, 2, 6-dibromopyridine (2g,8.4mmol), 3-bromobenzeneboronic acid (3,37g,16.8mmol) and K2CO3Mixing aqueous solution (30ml,2M), ethanol and toluene (80ml) in a three-neck flask to obtain a mixed solution, and discharging N220min, then Pd (PPh) is added rapidly3)4(100mg,0.42mmol), heated to 82 ℃ and reacted for 12 h. Cooling to room temperature after the reaction is finished, removing the solvent in the product through reduced pressure distillation, adding dichloromethane and distilled water to separate an organic layer and extracting a water layer for 3 times, and drying and filtering by using anhydrous magnesium sulfate after the extraction is finished. And then carrying out reduced pressure distillation and spin drying to remove the solvent, carrying out column chromatography separation and purification by adopting a wet method and using a mixed solvent with a ratio of 1:2 of DCM/PE as an eluent to finally obtain the compound 1 which is a transparent oily product, wherein the yield is about 79% (2.6 g).
Step two: preparation of 2, 6-bis (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pyridine (2)
The compound 1(2.6g,6.6mmol) described in the first step, diboronic acid ester (3.85g, 15.1mmol), potassium acetate (1.94g,19.8mmol) and tetrahydrofuran (60ml) were placed in a 250ml three-necked flask, and N was introduced thereinto2Pd (PPh) is added rapidly after 20min of exhaust3)2Cl2(100mg,0.198mmol) was stirred at 85 ℃ under reflux and reacted overnight. After the reaction is finished, tetrahydrofuran is removed through reduced pressure distillation, dichloromethane and water are added for extraction and separation of an organic layer for 3 times, then anhydrous magnesium sulfate is added for drying and filtration, after a solvent is removed through reduced pressure distillation, a product is purified through column chromatography separation (eluent dichloromethane) and an ethanol recrystallization method, and finally 2.55g of a product (compound 2) is obtained, wherein the yield is 80%.
Step three: preparation of 2, 4-diphenyl-6- (3- (6- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) pyridin-2-yl) phenyl) -1,3, 5-triazine (3)
2.55g (5.20mmol) of the compound 2, 1.55g (5.8mmol) of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine, 50ml of toluene, 20ml of ethanol and 20ml of Na are added2CO3The solution was added to a 100ml three-necked flask and N was introduced thereinto2Exhausting for 20min, and rapidly adding Pd (PPh)3)4(80mg,0.156mmol) and then heated (90 ℃ C.) to reflux and stirred overnight. After the reaction is finished, the solvent is removed by reduced pressure distillation, distilled water and dichloromethane are added for extraction for 3 times, anhydrous MgSO is4The product was purified by drying, filtration, washing with acetone, recrystallization from ethanol and column chromatography (eluent DCM: EOA ═ 8:1) to give compound 3 as a white product in 50% yield (1.5 g).
Step four: preparation of Compound Phen-2PhPy-TRZ (4)
Dissolving compound 3(1.5g, 2.5mmol)) and 3-bromo-1, 10-phenanthroline (0.71g, 2.75mmol) with toluene (30ml), adding ethanol (10ml) and K2CO3Solution (10ml, 2M) was charged with N2Pd (PPh) is added rapidly after 20min of exhaust3)4(50mg,0.075mmol) was heated (90 ℃ C.) to reflux and stirred, and reacted for 12 h. Cooling to room temperature after reaction, distilling under reduced pressure to remove solvent, adding dichloromethane and distilled water to separate organic layer and extracting water layer for 3 times, and extracting with anhydrous MgSO4Drying and filtering. The dichloromethane was removed by distillation under reduced pressure and spin-dried, and the product was purified by recrystallization from ethanol, column chromatography (eluent DCM: EOA ═ 6:1) and washing with methanol, acetone and dichloromethane to finally obtain 1.2g of the product (compound 4) in about 78% yield.
The asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ prepared in the examples was subjected to structural characterization and performance test as follows:
(1) nuclear magnetic resonance H spectrum
1H NMR(400MHz,CDCl3)δ9.56(d,J＝2.2Hz,1H),9.51(s,1H),9.23-9.22(m,1H),8.85-8.84(m,1H),8.79-8.77(m,4H),8.64(m,1H),8.50-8.48(m,2H),8.31-8.23(m,2H),7.97-7.92(m,2H),7.78-7.85(m,2H),7.76(s,2H),7.72(q,J＝8.0Hz,2H),7.64(dd,J＝4.0,8.0Hz,1H),7.57-7.49(m,6H).
FIG. 1 shows the NMR H spectrum of Phen-2PhPy-TRZ which is the asymmetrically substituted diphenylpyridine compound described in example 1.
(2) Thermodynamic properties
TGA2050(TA instruments) thermogravimetric analyzer in N2Performing Thermal Gravimetric Analysis (TGA) under a protection condition, wherein the heating rate is 20 ℃/min; thermal analyzer using NETZSCH DSC 204F1 at N2Differential Scanning Calorimetry (DSC) under atmosphere; the method comprises the following specific steps: heating to 394 deg.C at a heating rate of 10 deg.C/min with-30 deg.C as initial temperature, cooling to-30 deg.C at a cooling rate of 20 deg.C/min, holding for 5min, and heating at 10 deg.C/minThe temperature rise rate was tested to 394 ℃. The test results are shown in fig. 2. FIG. 2 is a thermal stability curve of the example asymmetrically substituted diphenylpyridine derivative Phen-2 PhPy-TRZ; wherein (a) and (b) in FIG. 2 are the thermogravimetry curve and the differential scanning calorimetry curve, respectively, of the asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ of example 1.
As can be seen from (a) in FIG. 2, the asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ of the present invention has 1% weight loss corresponding to 416 deg.C (i.e. the decomposition temperature of the material), 5% weight loss corresponding to 448.7 deg.C, and the material has high thermal stability.
As can be seen from fig. 2 (b), when the asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ of the present invention is heated in the first round, a distinct melting peak appears when the temperature reaches 270 ℃, which corresponds to the melting point of the material; while neither the first and second temperature reductions nor the crystallization or melting peak occurred and a distinct glass transition occurred at 129.3 ℃, corresponding to the glass transition temperature of the material. The results show that the material has high film morphology stability.
TRZ-m-Phen material (patent application No. 201810159745.0) lost 1% weight corresponding to a temperature of 339 deg.C (i.e., material decomposition temperature) and a glass transition temperature of 112 deg.C. Compared with the results, the asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ has higher thermal stability and morphological stability, namely the material has high intrinsic thermal stability and has the potential of being applied to stable devices.
(3) Physical Properties of light
FIG. 3 is a UV-VIS absorption spectrum of the asymmetrically substituted diphenylpyridine compound Phen-2PhPy-TRZ prepared in example 1. The film state absorption and emission of the Phen-2PhPy-TRZ have a certain red shift relative to the solution state, which is because the whole energy is weakened due to the large intermolecular force of the solid state; the thin film state absorption edge is located at 351nm, which corresponds to the optical band gap of the material being about 3.52 eV.
(4) Electroluminescent property
The asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ and Liq are doped to be used as an electron transport materialThe red light phosphorescence device has the structure of ITO/P008: P-dopant (100nm, 4%)/NPB (20nm)/Bebq2:Ir(MDQ)2(acac) (40nm, 5%)/Phen-2 PhPy-TRZ Liq (30nm 1:1)/Al (200 nm). Wherein P008 is P-DOPANT as hole injection layer, HTL as hole transport layer, Bebq2:Ir(MDQ)2(acac) as a light-emitting layer (Ir (MDQ)2(acac) is a red-phosphorescent complex, Bebq2As a host material), Liq is a lithium 8-hydroxyquinoline complex. .
The detailed preparation process of the device is as follows:
an Indium Tin Oxide (ITO) conductive glass substrate with the resistance of 10-20 omega/port is sequentially subjected to ultrasonic cleaning for 20min by deionized water, acetone, a detergent, deionized water and isopropanol. After drying in an oven, the ITO glass substrate treated in the way is evaporated with various organic functional layers and a metal Al cathode under the vacuum of 3 x 10 < -4 > Pa. The film thickness was measured using a Veeco Dektak150 step meter. The deposition rate of metal electrode evaporation and its thickness were determined using a Sycon Instrument thickness/velocimeter STM-100. The performance test results of the organic electroluminescent device are shown in fig. 4 to 6.
FIG. 4 is a current density-voltage-luminance curve of an organic red-phosphorescent organic electroluminescent device using the electron transport material Phen-2PhPy-TRZ prepared in example 1; FIG. 5 is a graph of luminous efficiency vs. luminance of a red phosphorescent organic electroluminescent device of the electron transport material Phen-2PhPy-TRZ prepared in example 1; FIG. 6 is a power efficiency-luminance curve of a red phosphorescent organic electroluminescent device using the electron transport material Phen-2PhPy-TRZ prepared in example 1.
As shown in FIGS. 4-6, the electron transport material Phen-2PhPy-TRZ prepared in example 1 was doped with Liq and then applied to red-emitting phosphorescent devices as an electron transport material in the range of 1000cd m-2The current efficiency and the power efficiency of the device reach 13.4cd/A and 10.6lm/W respectively under the brightness, and the front row exists in the same type of red light phosphorescence devices.
The material TRZ-m-Phen (patent application No. 201810159745.0) is doped with Liq and then applied to the same red light phosphorescent device, and the red light phosphorescent device can be known to be 1000cd m-2Current efficiency and power efficiency of the device at luminance12.1cd/A and 9.1lm/W, respectively. Comparison shows that the asymmetrically substituted diphenylpyridine derivative Phen-2PhPy-TRZ of the invention has higher efficiency after being doped with Liq. Meanwhile, compared with the commercially available material Phen-NaDPO (one-material company) (9.4cd/A and 5.9lm/W @1000cd m)-2) The electron transport material of the invention has higher efficiency under the same red light device structure, and is suspected to be derived from the Phen-2PhPy-TRZ: higher electron mobility of Liq.
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. An organic electron transport material characterized by: comprises more than one of unsymmetrical substituted diphenyl pyridine compounds with the structure of formula I or formula II;
2. the method for preparing an organic electron transport material according to claim 1, wherein: the method comprises the following steps:
(1) under the atmosphere of protective gas, reacting 2, 6-dihalopyridine and 3-halophenylboronic acid in an organic solvent under the action of a catalytic system, and performing subsequent treatment to obtain a dihalodiphenylpyridine compound;
the dihalodiphenylpyridine compound has the structure:
(2) reacting the dihalogenated diphenylpyridine compound obtained in the step (1) with diamyl diboron, and carrying out subsequent treatment to obtain an intermediate product containing boric acid ester;
the intermediate product containing borate has the structure:
(3) carrying out Suzuki coupling reaction on the intermediate product containing the boric acid ester obtained in the step (2) and a triazine compound, and carrying out subsequent treatment to obtain a triazine-containing intermediate product; the triazine compound is 2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-bis ((1,1' -biphenyl) -4-yl) -6-chloro-1, 3, 5-triazine;
the 2-chloro-4, 6-diphenyl-1, 3, 5-triazine has the structure
The structure of the 2, 4-bis ((1,1' -biphenyl) -4-yl) -6-chloro-1, 3, 5-triazine is
The triazine-containing intermediate product has the structure
(4) Under the action of a catalytic system, carrying out Suzuki coupling reaction on the triazine-containing intermediate product obtained in the step (3) and 3-bromo-1, 10-phenanthroline, and carrying out subsequent treatment to obtain an asymmetrically substituted diphenylpyridine compound which is marked as Phen-2PhPy-TRZ, namely a formula I or Phen-Py-BPTRZ, namely a formula II.
3. The method for preparing an organic electron transport material according to claim 2, wherein: the 2, 6-dihalopyridine in the step (1) is 2, 6-dibromopyridine, 2, 6-dichloropyridine or 2, 6-diiodopyridine; the 3-halogenophenylboronic acid is 3-bromobenzene boric acid, 3-chlorobenzene boric acid or 3-iodophenylboronic acid;
the reaction temperature in the step (1) is 80-82 ℃, and the reaction time is 10-15 h;
the reaction temperature in the step (2) is 80-85 ℃, and the reaction time is 8-12 h;
the reaction temperature in the step (3) is 80-90 ℃, and the reaction time is 10-12 h;
the reaction temperature in the step (4) is 85-95 ℃, and the reaction time is 10-15 h.
4. The method for preparing an organic electron transport material according to claim 2, wherein: the organic solvent in the step (1) is more than one of toluene, tetrahydrofuran, dioxane and DMSO; the catalytic system comprises a palladium catalyst, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium; the catalytic system further comprises a phase transfer agent and a basic compound; the molar ratio of the 2, 6-dihalopyridine to the 3-halophenylboronic acid to the tetrakis (triphenylphosphine) palladium is 1: (2-2.1): (0.01 to 0.06);
the reaction in the step (2) is carried out under the action of a catalytic system, wherein the catalytic system comprises a palladium catalyst, and the palladium catalyst is bis (triphenylphosphine) palladium dichloride; the molar ratio of the dihalogenated diphenylpyridine compound to the bis (triphenylphosphine) palladium dichloride and the bis (valeryl diboron) is 1: (2.2-2.4): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium; the catalytic system further comprises a basic compound;
the reaction in the step (3) is carried out in a catalytic system, wherein the catalytic system comprises a palladium catalyst, and the palladium catalyst is tetrakis (triphenylphosphine) palladium; the molar ratio of the intermediate product containing borate ester, the triazine compound and the palladium catalyst is 1: (1.1-1.3): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium; the reaction system also comprises a phase transfer agent and an alkaline aqueous solution;
the catalytic system in the step (4) comprises a palladium catalyst, wherein the palladium catalyst is tetrakis (triphenylphosphine) palladium; the molar ratio of the triazine-containing intermediate product to the 1, 10-phenanthroline and palladium catalyst is 1: (1.1-1.2): (0.01 to 0.04); the reaction takes an organic solvent as a reaction medium; the system of the reaction also comprises a phase transfer agent and an alkaline aqueous solution.
5. The method for preparing an organic electron transport material according to claim 4, wherein: in the step (1), the phase transfer agent is ethanol, and the alkaline compound is potassium carbonate;
in the step (2), the organic solvent is more than one of DMF, DMSO and tetrahydrofuran; the alkaline compound is potassium acetate;
in the step (3), the organic solvent is more than one of toluene, tetrahydrofuran, dioxane and DMSO; the phase transfer agent is ethanol, and the alkaline aqueous solution is a sodium carbonate aqueous solution;
in the step (4), the organic solvent is more than one of toluene, tetrahydrofuran, dioxane and DMSO, the phase transfer agent is ethanol, and the alkaline aqueous solution is potassium carbonate aqueous solution.
6. The method for preparing an organic electron transport material according to claim 2, wherein: the subsequent treatment in the step (1) is reaction completion, cooling, reduced pressure distillation, water and dichloromethane are added to extract a water layer, and an organic layer is dried, filtered, reduced pressure distilled by using anhydrous magnesium sulfate and then purified by a column chromatography separation method;
the subsequent treatment in the step (2) is to remove tetrahydrofuran by reduced pressure distillation after the reaction is finished, add water and dichloromethane for extraction, use anhydrous magnesium sulfate to dry, filter and reduce pressure distillation the organic layer, and then purify the product by column chromatography separation and recrystallization;
the subsequent treatment in the step (3) is to remove the solvent by reduced pressure distillation after the reaction is finished, then add water and dichloromethane to extract a water layer, dry and filter an organic layer by using anhydrous magnesium sulfate, and purify a product by solvent washing, recrystallization and column chromatography separation and purification methods;
and (4) the subsequent treatment refers to cooling to room temperature after the reaction is finished, distilling under reduced pressure to remove the solvent, adding water and dichloromethane to extract a water layer, drying an organic layer by anhydrous magnesium sulfate, filtering, distilling under reduced pressure to remove dichloromethane, and purifying the product by recrystallization, column chromatography separation and solvent washing methods.
7. A doped organic electron transport material, characterized by: comprising the organic electron transport material of claim 1 and a dopant which is a lithium 8-hydroxyquinoline complex.
8. Use of the organic electron transport material according to claim 1 or the doped organic electron transport material according to claim 7 for the preparation of an optoelectronic device.
9. Use according to claim 8, characterized in that: the photoelectric device is an organic electroluminescent device.
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