CN110016053B - Asymmetric substituted soluble pyridine derivative, preparation, n-doped electron transport layer and application - Google Patents

Asymmetric substituted soluble pyridine derivative, preparation, n-doped electron transport layer and application Download PDF

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CN110016053B
CN110016053B CN201910313376.0A CN201910313376A CN110016053B CN 110016053 B CN110016053 B CN 110016053B CN 201910313376 A CN201910313376 A CN 201910313376A CN 110016053 B CN110016053 B CN 110016053B
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朱旭辉
陈玲玲
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention belongs to the technical field of organic micromolecule functional materials, and discloses an asymmetrically substituted soluble pyridine derivative, a preparation method thereof, an n-doped electron transport layer and application thereof. The asymmetric substituted soluble pyridine derivative is more than one of a formula I or a formula II. The invention also discloses a preparation method of the asymmetrically substituted soluble pyridine derivative. The asymmetric substituted soluble pyridine derivative is used for preparing an organic electron transport material. The organic electron transport material comprises more than one of the asymmetrically substituted soluble pyridine derivatives. The n-doped electron transport layer is obtained by n-doping an organic electron transport material. The organic electron transport material has higher electron mobility, and an electron transport layer formed by n-doping is used for an organic electroluminescent device and has high luminous efficiency and high stability. The n-doped electron transport layer disclosed by the invention is applied to an organic electroluminescent device.

Description

Asymmetric substituted soluble pyridine derivative, preparation, n-doped electron transport layer and application
Technical Field
The invention belongs to the technical field of organic micromolecule functional materials, relates to an electron transport material, and particularly relates to an asymmetrically substituted soluble pyridine derivative, a preparation method thereof, an n-doped electron transport layer and application thereof. The asymmetric substituted soluble pyridine derivative is used for an organic electron transport material, and an n-doped electron transport layer is obtained by carrying out n-doping on the asymmetric substituted soluble pyridine derivative. The organic electron transport layer and the n-doped electron transport layer are applied to an organic light-emitting diode.
Background
Organic Light Emitting Diodes (OLEDs) have important applications in the fields of electroluminescent displays and lighting. Among them, the electron transport material is important for the organic light emitting diode, assists the injection of electrons from the cathode to the light emitting layer, and blocks the electrode from directly contacting the light emitting layer. In general, it is challenging to design high-purity, high-performance OLED electron transport materials, which need to consider many factors and complex trade-off relationships between them, such as glass transition temperature, carrier mobility, triplet energy level, electron injection, and hole blocking characteristics. Among them, the pursuit of high mobility often results in that the electron transport material is hardly soluble and difficult to purify. Further recent studies have shown that even trace amounts of halogen end groups remaining in the electron transport material will have a fatal effect on the stability of OLED devices (h. fujimoto et al, flame of material imprints in the hole-blocking layer on the lifetime of organic light-emitting diodes, appl. phys. lett.2016, volume 109).
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an asymmetric substituted soluble pyridine derivative and a preparation method thereof. The asymmetrically substituted soluble pyridine derivative is simple and soluble in preparation, has high glass transition temperature, can be used as an organic electron transport material, and can obtain a high-efficiency and high-stability organic electroluminescent device.
The invention also aims to provide application of the asymmetrically substituted soluble pyridine derivative. The asymmetric substituted soluble pyridine derivative is used for preparing an organic electron transport material. The organic electron transport material is more than one of the asymmetrically substituted soluble pyridine derivatives. The organic electron transport material has high glass transition temperature, is used for preparing electronic devices, and can obtain high-efficiency and high-stability organic electroluminescent devices.
It is yet another object of the present invention to provide an n-doped electron transport layer. The n-doped electron transport layer is obtained by n-doping using the above organic electron transport material. The organic micromolecule electron transport material provided by the invention has high electron mobility after n-doping.
The invention also aims to provide the application of the n-doped electron transport layer in devices such as organic electroluminescence devices.
The purpose of the invention is realized by the following technical scheme:
the asymmetrically substituted soluble pyridine derivative is more than one of the following formula I or formula II:
Figure BDA0002032264920000021
the preparation method of the asymmetrically substituted soluble pyridine derivative comprises the following steps:
(1) reacting diphenyl phosphonium chloride with dihalogenated benzene under the action of n-butyl lithium, and performing subsequent treatment to obtain an unoxidized bromine-containing intermediate product; the dihalogenated benzene is m-dibromobenzene, m-diiodobenzene or 1-bromo-3-iodobenzene;
the unoxidized bromine-containing intermediate product has the structure
Figure BDA0002032264920000022
(2) Carrying out hydrogen peroxide oxidation treatment on the unoxidized bromine-containing intermediate product obtained in the step (1), and carrying out subsequent treatment to obtain an oxidized bromine-containing intermediate product;
the structural formula of the oxidized bromine-containing intermediate product is shown in the specification
Figure BDA0002032264920000023
(3) Reacting the oxidized bromine-containing intermediate product obtained in the step (2) with bis (valeryl) diboron under the action of a palladium catalyst to obtain an intermediate product containing borate;
the intermediate product containing boric acid ester has the structure of
Figure BDA0002032264920000031
(4) Performing coupling reaction on the intermediate product containing the borate ester obtained in the step (3) and 2, 6-dibromopyridine under the action of a palladium catalyst to obtain bromide containing pyridine;
the structure of the bromide containing pyridine is
Figure BDA0002032264920000032
(5) 2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-di ([1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine and 3-bromobenzeneboronic acid are subjected to coupling reaction and subsequent treatment to obtain a bromine-containing intermediate;
the structure of the bromine-containing intermediate is
Figure BDA0002032264920000033
(6) Carrying out Suzuki reaction on the bromine-containing intermediate in the step (5) and the diboron pinacol ester, and carrying out subsequent treatment to obtain a borate intermediate;
the structure of the borate intermediate is
Figure BDA0002032264920000034
(7) And (3) carrying out coupling reaction on the bromide containing pyridine in the step (4) and the borate intermediate in the step (6) in a catalytic system, and carrying out subsequent treatment to obtain the asymmetrically substituted soluble pyridine derivative TRZ-Py-TPO (formula I) or BPTRZ-Py-TPO (formula II).
The reaction condition in the step (1) is room temperature reaction for 8-16 h; the molar ratio of dihalogenated benzene to n-butyllithium to diphenylphosphine chloride is 1: (1.1-1.3): (1.3-1.5); the reaction takes an organic solvent as a reaction medium; the organic solvent is preferably tetrahydrofuran;
the specific steps of the step (1) are as follows: in a protective atmosphere, dihalogenated benzene is dissolved in an organic solvent, the temperature is reduced to-70 to-78 ℃, n-butyllithium is added and mixed evenly, and diphenylphosphine chloride is added.
The reaction condition of the step (2) is room temperature reaction for 10-12 h, and the reaction takes an organic solvent as a reaction medium; the organic solvent is preferably dichloromethane;
the reaction in the step (3) is carried out for 3-4 h at 68-80 ℃, and the molar ratio of the oxidized bromine-containing intermediate product to the bis-valeryl diboron is 1: (1.3-1.5); the palladium catalyst is bis (triphenylphosphine) palladium dichloride; the molar ratio of the oxidized bromine-containing intermediate to the palladium catalyst is 1: (0.01-0.03); the reaction takes an organic solvent as a reaction medium; the organic solvent is preferably tetrahydrofuran; the system of the reaction also comprises an alkaline compound, preferably potassium acetate.
In the step (4), the molar ratio of the intermediate product containing boric acid ester, 2, 6-dibromopyridine and the palladium catalyst is 1: (1.0-1.1): (0.01-0.03); the palladium catalyst is tetrakis (triphenylphosphine) palladium; the system of the coupling reaction also comprises an alkaline aqueous solution and a phase transfer agent, wherein the alkaline aqueous solution is preferably a sodium carbonate aqueous solution, and the phase transfer agent is ethanol; the coupling reaction in the step (4) is carried out for 10-12 h at the temperature of 80-90 ℃, an organic solvent is used as a reaction medium in the reaction, and the organic solvent is preferably toluene.
The molar ratio of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-bis ([1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine to 3-bromobenzeneboronic acid in step (5) is 1: (1.0-1.1), the coupling reaction is carried out in a catalytic system, the catalytic system comprises a catalyst, the catalyst is a palladium catalyst, the palladium catalyst is tetrakis (triphenylphosphine) palladium, and the molar ratio of the 3-bromobenzoic acid to the catalyst is (1.0-1.1): (0.01-0.03); the catalytic system also comprises an alkaline aqueous solution and a phase transfer agent, wherein the alkaline aqueous solution is preferably a sodium carbonate aqueous solution, and the phase transfer agent is ethanol; the coupling reaction in the step (5) is carried out for 10-12 h at the temperature of 80-90 ℃; the reaction takes an organic solvent as a reaction medium, and the organic solvent is preferably toluene.
The reaction condition in the step (6) is that the reaction is carried out for 3-4 h at the temperature of 80-90 ℃; the molar ratio of the bromine-containing intermediate to the diboron acid pinacol ester is 1: (1.1-1.5); the reaction is carried out in 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 bromine-containing intermediate to the palladium catalyst is 1: (0.01-0.03); the reaction takes an organic solvent as a reaction medium, and the organic solvent is tetrahydrofuran; the catalytic system also comprises a basic compound, preferably potassium acetate.
The catalytic system in the step (7) comprises a catalyst, wherein the catalyst is a palladium catalyst, and the palladium catalyst is tetrakis (triphenylphosphine) palladium; the catalytic system also comprises an alkaline aqueous solution and a phase transfer agent, wherein the alkaline aqueous solution is a potassium carbonate solution or a sodium carbonate aqueous solution, and the phase transfer agent is ethanol; in the step (7), the molar ratio of the bromide containing pyridine to the borate intermediate is (1-1.2): 1; the coupling reaction in the step (7) is carried out for 10-16 h at 90-100 ℃, an organic solvent is used as a reaction medium in the reaction, and the organic solvent is preferably toluene.
The subsequent treatment in the step (1) is to add ethanol to terminate the reaction after the reaction is finished, to perform reduced pressure distillation, to mix with water, to extract with dichloromethane, to dry the organic layer with anhydrous magnesium sulfate and then to filter, to perform reduced pressure distillation to remove dichloromethane, and to separate by column chromatography.
And (2) the subsequent treatment in the step (2) is to add a sodium sulfite aqueous solution into the reaction product to reduce excessive hydrogen peroxide, extract the reaction product by using dichloromethane, dry an organic layer by using anhydrous magnesium sulfate, filter the organic layer, remove the dichloromethane by reduced pressure distillation, and separate the organic layer by using a column chromatography.
The subsequent treatment in the step (3) is to perform reduced pressure distillation on the reaction product, mix the reaction product with water, extract the reaction product with dichloromethane, dry an organic layer with anhydrous magnesium sulfate, filter the organic layer, remove dichloromethane through reduced pressure distillation, and separate the organic layer through column chromatography.
And (4) performing subsequent treatment by adding distilled water into the reaction product, separating an organic layer, extracting an aqueous layer by using dichloromethane, drying the extracted organic layer by using anhydrous magnesium sulfate, filtering, distilling under reduced pressure to remove dichloromethane, and separating by using a column chromatography.
And (5) performing subsequent treatment by adding distilled water into the reaction product, separating an organic layer, extracting an aqueous layer by using dichloromethane, drying the extracted organic layer by using anhydrous magnesium sulfate, filtering, distilling under reduced pressure to remove dichloromethane, and separating by using a column chromatography.
The subsequent treatment in the step (6) means that the reaction product is distilled under reduced pressure, dissolved in dichloromethane, added with distilled water and extracted with dichloromethane, the organic layer is dried over anhydrous magnesium sulfate and then filtered, dichloromethane is removed by distillation under reduced pressure, and the product is separated by column chromatography.
The subsequent treatment in the step (7) is to add distilled water to the reaction product, separate the organic layer, extract the aqueous layer with dichloromethane, dry the extracted organic layer with anhydrous magnesium sulfate, filter, distill under reduced pressure to remove dichloromethane, and separate by column chromatography.
An organic electron transport material comprises more than one of the asymmetrically substituted soluble pyridine derivatives, preferably more than one of the asymmetrically substituted soluble pyridine derivatives in the formula I or the formula II.
The n-doped electron transport layer is obtained by n-doping the organic electron transport material with a dopant.
The dopant is preferably a lithium 8-hydroxyquinoline complex (Liq); the doping amount of the dopant satisfies the following conditions: the mass ratio of the dopant to the organic electron transport material is (0.3-2): 1.
the organic electron transport material is applied to an organic electroluminescent device, in particular to a phosphorescent device.
The n-doped electron transport layer is applied to an organic electroluminescent device.
The principle of the invention is as follows:
the invention introduces 2,4, 6-triphenyl-1, 3, 5-triazine on diphenyl (3- (pyridine-2-yl) phenyl) phosphine oxide group
Figure BDA0002032264920000061
Or 2, 4-bis ([1,1' -biphenyl)]-4-yl) -6-phenyl-1, 3, 5-triazine
Figure BDA0002032264920000062
The unit cell obtains TRZ-Py-TPO and BPTRZ-Py-TPO which are organic micromolecule electron transport materials. 2,4, 6-triphenyl-1, 3, 5-triazine units and 2, 4-bis ([1,1' -biphenyl)]The 4-yl) -6-phenyl-1, 3, 5-triazine unit enables the organic small molecule electron transport material to have high mobility; and the aryl phosphine oxide group can improve the solubility of the compound in common organic solvents (such as dichloromethane, chloroform, ethanol, ethyl acetate and the like), and is beneficial to the purification of materials.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the organic electron transport material has good thermal stability, wherein the temperature of TRZ-Py-TPO with weight loss of 1% is 370 ℃, and the temperature of BPTRZ-Py-TPO with weight loss of 1% is 470 ℃; the glass transition temperatures of the two compounds are 102 ℃ and 123 ℃ respectively;
(2) the organic electron transport material has the characteristics of simple structure and synthesis preparation, and has good solubility, for example, the solubility in dichloromethane is more than 100mg/ml, and the solubility in ethanol is more than 10 mg/ml;
(3) the organic electron transport material has higher electron mobility after n-doping Liq, and the electron mobility of TRZ-Py-TPO is 4.99 × 10-6-4.58×10-5cm2·V-1·s-1(@2-5×105V·cm-1) BPTRZ-Py-TPO has higher electron mobility (4.66 × 10)-5-3.21×10-4cm2·V-1·s-1@2-5×105V·cm-1) All have higher mobility than Phen-NaDPO Liq (9.3 × 10)-7-6.6×10-6cm2·V-1·s-1@2-5×105V·cm-1(ii) a Patent ZL201310275234.2, a molecular material of alcohol-soluble cathode buffer layer containing triaryl phosphorus oxygen and nitrogen heterocyclic functional groups and a synthetic method thereof);
(4) the organic electron transport material is applied to a green light phosphorescence device after n-doping Liq to obtain higher device efficiency and stability: at 1000 cd.m-2The current efficiency and the power efficiency of the TRZ-Py-TPO device reach 72.1cd/A and 75.5m/W respectively, and the current efficiency and the power efficiency of the BPTRZ-Py-TPO device reach 77.4cd/A and 86.8lm/W respectively; at an initial luminance of 1000 cd-m under constant current drive-2After about 640h of operation at brightness of (a), there was substantially no degradation in brightness.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of TRZ-Py-TPO as an organic electron transport material of example 1;
FIG. 2 is a thermal stability curve of the organic electron transporting material TRZ-Py-TPO of example 1; wherein FIG. 2a and FIG. 2b are the thermogravimetric curve and the differential scanning calorimetry curve, respectively, of the organic electron transporting material TRZ-Py-TPO of example 1;
FIG. 3 shows the UV-VIS absorption spectrum of TRZ-Py-TPO as an organic electron transport material of example 1;
FIG. 4 is a characteristic curve of electron mobility-electric field strength of the organic electron transport material TRZ-Py-TPO prepared in example 1 and Liq doped at a mass ratio of 1:1 n-;
FIG. 5 is a current density-voltage-luminance curve of a top-emission green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1;
FIG. 6 is a current efficiency-luminance curve (i.e., a luminous efficiency-luminance curve) of a top-emission green phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1;
FIG. 7 is a graph of power efficiency versus luminance for a top-emitting green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1;
FIG. 8 is a graph of luminance versus time for a top-emitting green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1;
FIG. 9 is a NMR hydrogen spectrum of BPTRZ-Py-TPO of example 2;
FIG. 10 is a thermal stability curve of BPTRZ-Py-TPO, an organic small molecule electron transport material of example 2; wherein, FIG. 10a and FIG. 10b are the thermogravimetric curve and the differential scanning calorimetry curve of BPTRZ-Py-TPO as the small molecule electron transport material of example 2, respectively;
FIG. 11 is a UV-VISIBLE ABSORPTION SPECTRUM OF BPTRZ-Py-TPO, an organic electron transport material according to example 2;
FIG. 12 is a characteristic curve of electron mobility-electric field strength of the organic electron transport materials BPTRZ-Py-TPO prepared in example 2 doped with Liq at a mass ratio of 1:1 n-;
FIG. 13 is a current density-voltage-luminance curve of a top emission green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2;
fig. 14 is a current efficiency-luminance curve (i.e., a luminous efficiency-luminance curve) of a top-emission green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2;
FIG. 15 is a graph of power efficiency versus luminance for a top-emitting green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2;
fig. 16 is a luminance-time curve of a top emission green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The structural formula of the organic electron transport material TRZ-Py-TPO of this example is:
Figure BDA0002032264920000081
the preparation method of the organic electron transport material TRZ-Py-TPO of the embodiment comprises the following steps:
step 1 preparation of (3-bromophenyl) diphenylphosphine (1)
Figure BDA0002032264920000082
In N21, 3-dibromobenzene (3.5g,15.04mmol) was dissolved in dry tetrahydrofuran (200mL) under an atmosphere and cooled to-78 ℃; subsequently, n-butyllithium (2.5M n-hexane solution, 7.8mL,19.55mmol) was added dropwise via syringe; after 30 minutes diphenylphosphine chloride (4.1mL,22.56mmol)) was added via syringe; the mixed solution is returned to the room temperature and is continuously stirred for 12 hours; after the reaction is finished, adding ethanol to terminate the reaction, removing the solvent under reduced pressure, pouring the reaction mixture into water, and extracting with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure, and then separated by a silica gel column, and the eluent was a mixed solvent of petroleum ether and dichloromethane (4:1v/v), to give (3-bromophenyl) diphenylphosphine (1) as a white solid.
Step 2 preparation of (3-bromophenyl) diphenylphosphine oxide (2)
Figure BDA0002032264920000091
Adding 30% hydrogen peroxide (6mL) in mass concentration to a dichloromethane (20mL) solution of compound (1) (3-bromophenyl) diphenylphosphine (4.18g,12.29mmol), and stirring at room temperature for 12 h; after the reaction is finished, pouring a sodium sulfite aqueous solution into the reaction mixture to reduce excessive hydrogen peroxide, and extracting with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, the solvent was removed under reduced pressure and separated by a silica gel column, and dichloromethane was used as an eluent to obtain (3-bromophenyl) diphenylphosphine oxide (2) as a white solid in a yield of 96% (4.2 g).
Step 3, preparation of Diphenyl (3- (4,4,5, 5-tetramethyl-1, 3, 2-2-dioxaboryl) phenyl) phosphine oxide (3)
Figure BDA0002032264920000092
In N2Bis (triphenylphosphine) palladium dichloride (80mg,0.11mmol) was added to a mixture of compound (2) (3-bromophenyl) diphenylphosphine oxide (2.3g,6.44mmol), bis (valeryl) diboron (2.45g,9.66mmol) and potassium acetate (1.9g,19.32mmol) in tetrahydrofuran (60mL) under an atmosphere, and the mixture was heated under reflux for 3 hours; after cooling to room temperature, removing the solvent under reduced pressure, pouring the reaction mixture into water, and extracting with dichloromethane; the organic layer was dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure, followed by separation with a silica gel column, and the eluent was a mixed solvent of dichloromethane and ethyl acetate (4:1v/v), to give diphenyl (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaboryl) phenyl) phosphine oxide (compound 3) as a white solid in 94% yield (2.44 g).
Step 4 preparation of (3- (6-bromopyridin-2-yl) phenyl) diphenylphosphine oxide (4)
Figure BDA0002032264920000101
In N2Tetrakis (triphenylphosphine) palladium (70mg) was added to a mixture of compound (3) (2.44g, 6.03mmol), 2, 6-dibromopyridine (1.43g, 6.03mmol), ethanol (8ml) and aqueous sodium carbonate (2M, 8ml) in toluene (100ml) under an atmosphere, and the reaction was stirred at 90 ℃ for 12 hours; after the reaction was completed, the toluene layer was separated by adding distilled water to the reaction mixture, the aqueous layer was extracted with dichloromethane, the extracted organic layer was dried over anhydrous magnesium sulfate and filtered, dichloromethane was distilled off under reduced pressure, and the obtained crude product was separated by column chromatography, using a mixed solvent of dichloromethane and ethyl acetate (3:1v/v) as an eluent, to obtain a white solid (compound 4) in a yield of 80% (2.1 g).
Step 5, preparation of 2- (3-bromophenyl) -4, 6-diphenyl-1, 3, 5-triazine (5)
Figure BDA0002032264920000102
In N2Tetrakis (triphenylphosphine) palladium (110mg) was added to a mixture of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (4.0g, 14.94mmol), 3-bromo-phenylboronic acid (3.0g,14.94mmol), ethanol (15ml) and aqueous sodium carbonate (2M, 15ml) in toluene (100ml) under an atmosphere, and the reaction was stirred at 90 ℃ for 12 hours; after the reaction was completed, the toluene layer was separated by adding distilled water to the reaction mixture, the aqueous layer was extracted with dichloromethane, the extracted organic layer was dried over anhydrous magnesium sulfate and filtered, dichloromethane was distilled off under reduced pressure, the obtained crude product was separated by column chromatography, and the eluent was petroleum ether to give a white solid (compound 5) in a yield of 77.6% (4.5 g).
Step 6, 2, 4-Diphenyl-6- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -1,3, 5-triazine (6) preparation
Figure BDA0002032264920000103
In N2Bis (triphenylphosphine) palladium dichloride (80mg,0.11mmol) was added to a mixture of compound 5(4.5g, 11.59mmol), pinacol diboron diboride (4.3g, 17.38mmol), potassium acetate (3.41g, 34.77mmol) in tetrahydrofuran (100ml) under an atmosphere,stirring and reacting for 3 hours at 80 ℃; after the reaction was completed, tetrahydrofuran was distilled off under reduced pressure, dissolved in dichloromethane, distilled water was added and extracted with dichloromethane, the resulting organic layer was dried over anhydrous magnesium sulfate and filtered, dichloromethane was distilled off under reduced pressure, the resulting crude product was separated by column chromatography, and the eluent was a mixed solvent of petroleum ether and dichloromethane (2:1v/v) to give a white solid (compound 6) in a yield of 93% (4.7 g).
Step 7 preparation of (3- (6- (3- (6, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) pyridin-2-yl) phenyl) diphenylphosphine oxide (TRZ-Py-TPO)
Figure BDA0002032264920000111
In N2Tetrakis (triphenylphosphine) palladium (110mg) was added to a mixture of compound 4(2.99g, 6.89mmol), compound 6(3.0g,6.89mmol), ethanol (7ml) and aqueous potassium carbonate (2M, 7ml) in toluene (50ml) under an atmosphere, and the reaction was stirred at 90 ℃ for 16 hours; after completion of the reaction, the toluene layer was separated by adding distilled water to the reaction mixture, the aqueous layer was extracted with dichloromethane, the extracted organic layer was dried over anhydrous magnesium sulfate and filtered, dichloromethane was distilled off under reduced pressure, and the obtained crude product was separated by column chromatography using a mixed solvent of dichloromethane and ethyl acetate (4:1v/v) as an eluent to obtain a white solid (TRZ-Py-TPO) in a yield of 61% (2.8 g).
The organic small molecule electron transport material TRZ-Py-TPO prepared in example 1 was subjected to structural characterization and performance testing as follows:
(1) hydrogen spectrum of nuclear magnetic resonance
1H NMR(400MHz,CDCl3)9.43(s,1H),8.83(ddd,J＝12.8,8.0,1.5Hz,5H),8.54(dd,J＝7.7,1.3Hz,1H),8.47(d,J＝12.7Hz,1H),8.38(dd,J＝7.7,1.1Hz,1H),7.96–7.86(m,2H),7.80–7.68(m,7H),7.67–7.53(m,9H),7.53–7.43(m,4H).
FIG. 1 shows the NMR spectrum of TRZ-Py-TPO as an organic electron transport material in example 1.
(2) Thermodynamic properties
Thermogravimetric analysis (TGA) was determined on a TGA2050(TA instruments) thermogravimetric analyzer with nitrogen blanket at a temperature rise rate of 20 ℃/min; differential Scanning Calorimetry (DSC) Using a NETZSCH DSC204F1 thermal analyzer, in a nitrogen atmosphere, from-30 deg.C, the temperature is raised to 350 deg.C at a rate of 10 deg.C/min, then lowered to-30 deg.C at a rate of 20 deg.C/min, and the temperature is maintained for 5min, and then the temperature is raised to 350 deg.C at a rate of 10 deg.C/min. The test results are shown in fig. 2. FIG. 2 is a thermal stability curve of the organic electron transporting material TRZ-Py-TPO of example 1; wherein FIG. 2a and FIG. 2b are the thermogravimetry curve and the differential scanning calorimetry curve of the organic electron transport material TRZ-Py-TPO of example 1, respectively.
As shown in FIG. 2a, the thermal weight loss curve of TRZ-Py-TPO shows that the temperature at 1% weight loss is 370 ℃, and the thermal stability is high.
As shown by the differential scanning calorimetry curve of FIG. 2b, compound TRZ-Py-TPO showed a distinct melting peak during the first heating run, corresponding to a melting point of 214 ℃. The organic small molecule electron transport material TRZ-Py-TPO shows an un-crystallized peak and a melting peak in the first round of temperature reduction and the second round of temperature rise, but shows obvious glass transition at 102 ℃.
(3) Physical Properties of light
FIG. 3 shows the UV-visible absorption spectrum (emission intensity vs. wavelength, absorbance vs. wavelength) of the organic electron transport material TRZ-Py-TPO prepared in example 1. From the absorption spectrum in fig. 3, the optical band gap can be determined to be 3.63eV from the absorption edge.
(4) Electron mobility
A single-electron device (ITO/TRZ-Py-TPO: Liq (50% wt, 150nm)/Al) was prepared, and the electron mobility was calculated by the space charge limited current SCLC method according to the current density-voltage curve. Liq is an 8-hydroxyquinoline lithium complex. 50% wt means the mass ratio of Liq to TRZ-Py-TPO is 1: 1.
The detailed preparation process of the single-electron 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 oven drying, the treated ITO glass substrate is placed in 3×10-4And (3) evaporating each organic functional layer and the metal Al cathode under the vacuum of 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. FIG. 4 is a graph showing the electron mobility-electric field intensity curves of the organic electron transport material TRZ-Py-TPO prepared in example 1 and Liq doped at a mass ratio of 1:1 n-.
As shown in FIG. 4, the electron mobility of the small molecule organic electron transport material TRZ-Py-TPO of this example is 4.99 × 10-6-4.58×10-5cm2·V-1·s-1(@2-5×105V·cm-1)。
(5) Characterization of organic electroluminescent devices by vacuum deposition as n-doped electron transport layer
Using the organic small-molecule electron transport material TRZ-Py-TPO n-doped Liq prepared in example 1 as an electron transport layer, a device structure of Ag/ITO/P008: F4-TCNQ (147nm, 4%)/NPB (15nm)/EBL-1(5nm)/HOST-09: HOST-08: GD-L1(30nm,0.5:0.5: 15%)/TRZ-Py-TPO: Liq (30nm,1:1)/Mg: Ag (15nm,1:9)/CP501(70nm) was prepared, and other organic materials except for the organic electron transport material were commercially available directly, wherein P008: F4-TCNQ was used as a hole injection layer (Beijing Ding materials Co., Ltd.), NPB was used as a hole transport layer, HOST09: HOST 3: GD-L1 was used as a light emitting layer (84: phosphor complex, Host 84: Host 19: Chijing optical co., LTP 19: WO 35: Chin 19. Mitsu technologies, Mitsu-L Mitsu corporation), and Host 3: GD-L1 was prepared as a light emitting layer, a device was prepared by Mitsunami technologies, a device structure of a semiconductor thin film, a semiconductor device structure of a semiconductor device, a semiconductor device structure of a semiconductor device-4S m-1。
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 oven drying, the treated ITO glass is driedThe substrate is at 3 × 10-4And (3) evaporating each organic functional layer and the metal Al cathode under the vacuum of 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. 5 to 8.
FIG. 5 is a current density-voltage-luminance curve of a top-emission green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1; FIG. 6 is a graph of current efficiency versus luminance for a top-emitting green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1; FIG. 7 is a graph of power efficiency versus luminance for a top-emitting green-emitting phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1; fig. 8 is a graph of luminance versus time for a top-emission green phosphorescent organic electroluminescent device using the organic electron transport material TRZ-Py-TPO prepared in example 1.
As shown in FIGS. 5 to 7, the organic electroluminescent device fabricated by vacuum deposition was prepared by doping Liq with TRZ-Py-TPO n-as an electron transport layer and then depositing the layer at 1000cd m-2The current efficiency and the power efficiency of the green phosphorescence reach 72.1cd/A and 75.5m/W respectively at the luminance of (1).
Preliminary device stability tests showed (see FIG. 8) that the top-emitting green phosphorescent device prepared from TRZ-Py-TPO was driven at an initial luminance of 1000cd m under constant current-2The brightness is not basically reduced after the operation for about 640 hours.
The above results indicate that the doped electron transport material TRZ-Py-TPO can achieve high luminous efficiency and high stability.
Example 2
The organic molecular electron transport material BPTRZ-Py-TPO of this example has the following structural formula:
Figure BDA0002032264920000141
the preparation method of organic molecular electron transport material BPTRZ-Py-TPO of the embodiment comprises the following steps:
steps 1 to 4 are the same as in example 1.
Step preparation of 5, 2, 4-bis ([1,1' -biphenyl ] -4-yl) -6- (3-bromophenyl) -1,3, 5-triazine (5)
Figure BDA0002032264920000142
The procedure was similar to that of example 1 and will not be repeated here, the yield being 78% (5.0 g).
Step 6 preparation of 2, 4-bis ([1,1' -biphenyl ] -4-yl) -6- (3- (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) phenyl) -1,3, 5-triazine (6)
Figure BDA0002032264920000151
The procedure was similar to that of example 1 and will not be repeated here, giving a yield of 81.5% (4.4 g).
Step 7 preparation of (3- (6- (3- (4, 6-bis ([1,1' -biphenyl ] -4-yl) -1,3, 5-triazin-2-yl) phenyl) pyridin-2-yl) phenyl) diphenylphosphine oxide (BPTRZ-Py-TPO)
Figure BDA0002032264920000152
The procedure was similar to that of example 1 and will not be repeated here, the yield being 77% (3.2 g).
The organic small molecule electron transport material BPTRZ-Py-TPO prepared in example 2 is subjected to structural characterization and performance test as follows:
(1) hydrogen spectrum of nuclear magnetic resonance
1H NMR(400MHz,CDCl3)9.43(s,1H),8.87(m,J＝8.1,6.4Hz,5H),8.51(m,J＝21.3,10.2Hz,2H),8.40(d,J＝7.9Hz,1H),7.92(m,J＝7.8Hz,2H),7.82(d,J＝8.5Hz,4H),7.79–7.69(m,11H),7.66(td,J＝7.6,3.2Hz,1H),7.57(m,J＝7.3,1.4Hz,2H),7.54–7.46(m,8H),7.46–7.39(m,2H).
FIG. 9 shows the NMR spectrum of BPTRZ-Py-TPO as an organic electron transport material in example 2.
(2) Thermodynamic properties
Thermogravimetric analysis (TGA) was determined on a TGA2050(TA instruments) thermogravimetric analyzer with nitrogen blanket at a temperature rise rate of 20 ℃/min; differential Scanning Calorimetry (DSC) Using a NETZSCH DSC204F1 thermal analyzer, in a nitrogen atmosphere, from-30 deg.C, the temperature is raised to 450 deg.C at a rate of 10 deg.C/min, then lowered to-30 deg.C at a rate of 20 deg.C/min, and the temperature is maintained for 5min, and then the temperature is raised to 450 deg.C at a rate of 10 deg.C/min. The test results are shown in fig. 10. FIG. 10 is a thermal stability curve of BPTRZ-Py-TPO, an organic electron transport material of example 2; wherein FIG. 10a and FIG. 10b are the thermogravimetry curve and the differential scanning calorimetry curve of the organic electron transport material BPTRZ-Py-TPO of example 2, respectively.
As shown in FIG. 10a, the thermal weight loss curve of BPTRZ-Py-TPO shows that the temperature at which 1% weight loss occurs is 470 ℃ and the thermal stability is high.
As shown by the differential scanning calorimetry curve of FIG. 10b, the compound BPTRZ-Py-TPO showed a distinct melting peak at the first heating cycle, corresponding to a melting point of 262 ℃. In the second heating process, the organic micromolecule electron transport material BPTRZ-Py-TPO has obvious crystallization peak and melting peak, the crystallization temperature is 209 ℃, and the melting point is 261 ℃. In addition, BPTRZ-Py-TPO showed a clear glass transition, corresponding to a glass transition temperature of 123 ℃.
(3) Physical Properties of light
FIG. 11 shows the UV-VIS absorption spectrum of BPTRZ-Py-TPO, an organic electron transport material prepared in example 2. From the absorption spectrum in fig. 11, the optical band gap can be determined to be 3.38eV from the absorption edge.
(4) Electron mobility
FIG. 12 is a graph showing the electron mobility-electric field intensity curves of the organic electron transport materials BPTRZ-Py-TPO prepared in example 2 and Liq doped at a mass ratio of 1:1 n-.
As shown in FIG. 12, the electron mobility of BPTR Z-Py-TPO, which is an organic electron transport material of this embodiment, is 4.66 × 10 according to SCLC calculation-5-3.21×10-4cm2·V-1·s-1(@2-5×105V·cm1)。
(5) Characterization of organic electroluminescent devices by vacuum deposition as n-doped electron transport layer
The organic small molecule electron transport material BPTRZ-Py-TPO n-doped Liq prepared in example 2 was used as an electron transport layer to prepare a device structure: Ag/ITO/P008: F4-TCNQ (147nm, 4%)/NPB (15n m)/EBL-1(5nm)/HOST-09: HOST-08: GD-L1(30nm,0.5:0.5: 15%)/BPTRZ-Py-TPO: Liq (30nm,1:1)/Mg: Ag (15nm,1:9)/CP501(70 nm).
The preparation process of the device is the same as that of the embodiment 1, and the performance test results of the organic electroluminescent device are shown in fig. 13-16.
FIG. 13 is a current density-voltage-luminance curve of a top emission green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2; FIG. 14 is a graph of current efficiency versus luminance for a top-emitting green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2; FIG. 15 is a graph of power efficiency versus luminance for a top-emitting green phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2; FIG. 16 is a graph of luminance versus time for a top-emitting green-emitting phosphorescent organic electroluminescent device using the organic electron transport material BPTRZ-Py-TPO prepared in example 2
As shown in FIGS. 13 to 15, the organic electroluminescent element produced by vacuum deposition was formed by doping Liq with BPTRZ-Py-TPO n-as an electron transport material and then forming an electron transport layer of 1000cd m-2The current efficiency and the power efficiency of the green phosphorescence reach 77.4cd/A,86.8lm/W, respectively.
As shown in FIG. 16, the top-emitting green phosphorescent device prepared from BPTRZ-Py-TPO was driven at a constant current at an initial luminance of 1000 cd.m-2The brightness is not substantially reduced after about 640 hours of operation.
The above results indicate that the doped electron transport material BPTRZ-Py-TPO can achieve high luminous efficiency and high stability.
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: the pyridine derivative comprises more than one of unsymmetrically substituted soluble pyridine derivatives, wherein the unsymmetrically substituted soluble pyridine derivatives are represented by more than one of the following formulas I or II:
Figure FDA0002489966780000011
2. the organic electron transport material of claim 1, wherein: the preparation method of the asymmetrically substituted soluble pyridine derivative comprises the following steps:
(1) reacting diphenyl phosphonium chloride with dihalogenated benzene under the action of n-butyl lithium, and performing subsequent treatment to obtain an unoxidized bromine-containing intermediate product; the dihalogenated benzene is m-dibromobenzene or 1-bromo-3-iodobenzene;
the unoxidized bromine-containing intermediate product has the structure
Figure FDA0002489966780000012
(2) Carrying out hydrogen peroxide oxidation treatment on the unoxidized bromine-containing intermediate product obtained in the step (1), and carrying out subsequent treatment to obtain an oxidized bromine-containing intermediate product;
the structural formula of the oxidized bromine-containing intermediate product is shown in the specification
Figure FDA0002489966780000013
(3) Reacting the oxidized bromine-containing intermediate product obtained in the step (2) with bis (valeryl) diboron under the action of a palladium catalyst to obtain an intermediate product containing borate;
the intermediate product containing boric acid ester has the structure of
Figure FDA0002489966780000014
(4) Performing coupling reaction on the intermediate product containing the borate ester obtained in the step (3) and 2, 6-dibromopyridine under the action of a palladium catalyst to obtain bromide containing pyridine;
the structure of the bromide containing pyridine is
Figure FDA0002489966780000021
(5) 2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-di ([1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine and 3-bromobenzeneboronic acid are subjected to coupling reaction and subsequent treatment to obtain a bromine-containing intermediate;
the structure of the bromine-containing intermediate is
Figure FDA0002489966780000022
(6) Carrying out Suzuki reaction on the bromine-containing intermediate in the step (5) and the diboron pinacol ester, and carrying out subsequent treatment to obtain a borate intermediate;
the structure of the borate intermediate is
Figure FDA0002489966780000023
(7) In a catalytic system, coupling reaction is carried out on the bromide containing pyridine in the step (4) and the borate intermediate in the step (6), and subsequent treatment is carried out to obtain an asymmetric substituted soluble pyridine derivative represented as TRZ-Py-TPO, wherein the structure of the derivative is represented as formula I or BPTRZ-Py-TPO, and the structure of the derivative is represented as formula II;
Figure FDA0002489966780000024
3. the organic electron transport material of claim 2, wherein: the reaction condition in the step (1) is room temperature reaction for 8-16 h; the molar ratio of dihalogenated benzene to n-butyllithium to diphenylphosphine chloride is 1: (1.1-1.3): (1.3-1.5); the reaction takes an organic solvent as a reaction medium;
the reaction condition of the step (2) is room temperature reaction for 10-12 h, and the reaction takes an organic solvent as a reaction medium;
the reaction in the step (3) is carried out for 3-4 h at 68-80 ℃, and the molar ratio of the oxidized bromine-containing intermediate product to the bis-valeryl diboron is 1: (1.3-1.5); the palladium catalyst is bis (triphenylphosphine) palladium dichloride; the molar ratio of the oxidized bromine-containing intermediate to the palladium catalyst is 1: (0.01-0.03); the reaction takes an organic solvent as a reaction medium; the system of the reaction further comprises a basic compound;
in the step (4), the molar ratio of the intermediate product containing boric acid ester, 2, 6-dibromopyridine and the palladium catalyst is 1: (1.0-1.1): (0.01-0.03); the palladium catalyst is tetrakis (triphenylphosphine) palladium; the system of the coupling reaction also comprises an alkaline aqueous solution and a phase transfer agent; the coupling reaction in the step (4) is carried out for 10-12 h at the temperature of 80-90 ℃, and an organic solvent is used as a reaction medium;
the molar ratio of 2-chloro-4, 6-diphenyl-1, 3, 5-triazine or 2, 4-bis ([1,1' -biphenyl ] -4-yl) -6-chloro-1, 3, 5-triazine to 3-bromobenzeneboronic acid in step (5) is 1: (1.0-1.1), the coupling reaction is carried out in a catalytic system, the catalytic system comprises a catalyst, the catalyst is a palladium catalyst, the palladium catalyst is tetrakis (triphenylphosphine) palladium, and the molar ratio of the 3-bromobenzoic acid to the catalyst is (1.0-1.1): (0.01-0.03); the catalytic system further comprises an aqueous alkaline solution and a phase transfer agent; the coupling reaction in the step (5) is carried out for 10-12 h at the temperature of 80-90 ℃; the reaction takes an organic solvent as a reaction medium;
the reaction condition in the step (6) is that the reaction is carried out for 3-4 h at the temperature of 80-90 ℃; the molar ratio of the bromine-containing intermediate to the diboron acid pinacol ester is 1: (1.1-1.5); the reaction is carried out in 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 bromine-containing intermediate to the palladium catalyst is 1: (0.01-0.03); the reaction takes an organic solvent as a reaction medium; the catalytic system further comprises a basic compound;
the catalytic system in the step (7) comprises a catalyst, wherein the catalyst is a palladium catalyst, and the palladium catalyst is tetrakis (triphenylphosphine) palladium; the catalytic system further comprises an alkaline aqueous solution and a phase transfer agent, wherein the molar ratio of the bromide containing pyridine to the borate intermediate in the step (7) is (1-1.2): 1; the coupling reaction in the step (7) is carried out for 10-16 h at the temperature of 90-100 ℃, and an organic solvent is used as a reaction medium.
4. The organic electron transport material of claim 3, wherein: in the step (3), the alkaline compound is potassium acetate;
in the step (4), the alkaline aqueous solution is a sodium carbonate aqueous solution, and the phase transfer agent is ethanol;
in the step (5), the alkaline aqueous solution is a sodium carbonate aqueous solution, and the phase transfer agent is ethanol;
in the step (6), the alkaline compound is potassium acetate;
in the step (7), the alkaline aqueous solution is a potassium carbonate solution or a sodium carbonate aqueous solution, and the phase transfer agent is ethanol.
5. The organic electron transport material of claim 2, wherein: the subsequent treatment in the step (1) is to add ethanol to terminate the reaction after the reaction is finished, to carry out reduced pressure distillation, to mix with water, to extract with dichloromethane, to dry an organic layer with anhydrous magnesium sulfate and then to filter, to carry out reduced pressure distillation to remove dichloromethane, and to separate by column chromatography;
the subsequent treatment in the step (2) is to add sodium sulfite aqueous solution into the reaction product to reduce excessive hydrogen peroxide, extract the hydrogen peroxide by dichloromethane, dry an organic layer by anhydrous magnesium sulfate and then filter the organic layer, remove dichloromethane by reduced pressure distillation, and separate the organic layer by column chromatography;
the subsequent treatment in the step (5) is to add distilled water into the reaction product, separate an organic layer, extract an aqueous layer by dichloromethane, dry the extracted organic layer by anhydrous magnesium sulfate, filter, remove dichloromethane by reduced pressure distillation, and separate by column chromatography;
the subsequent treatment in the step (6) is to perform reduced pressure distillation on the reaction product, dissolve the reaction product by dichloromethane, add distilled water and extract by dichloromethane, dry an organic layer by anhydrous magnesium sulfate and then filter the organic layer, remove the dichloromethane by reduced pressure distillation, and separate the organic layer by column chromatography;
the subsequent treatment in the step (7) is to add distilled water to the reaction product, separate the organic layer, extract the aqueous layer with dichloromethane, dry the extracted organic layer with anhydrous magnesium sulfate, filter, distill under reduced pressure to remove dichloromethane, and separate by column chromatography.
6. Use of the organic electron transport material according to claim 1 in an organic electroluminescent device.
7. An n-doped electron transport layer, comprising: is obtained by n-doping an organic electron-transporting material with a dopant, said organic electron-transporting material being as defined in claim 1.
8. The n-doped electron transport layer of claim 7, wherein: the dopant is an 8-hydroxyquinoline lithium complex.
9. Use of an n-doped electron transport layer according to claim 7 or 8 in an organic electroluminescent device.
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