CN113173927A - Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof - Google Patents

Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof Download PDF

Info

Publication number
CN113173927A
CN113173927A CN202110524493.9A CN202110524493A CN113173927A CN 113173927 A CN113173927 A CN 113173927A CN 202110524493 A CN202110524493 A CN 202110524493A CN 113173927 A CN113173927 A CN 113173927A
Authority
CN
China
Prior art keywords
formula
substituted
unsubstituted
compound shown
pyridyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN202110524493.9A
Other languages
Chinese (zh)
Inventor
方一文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang Wanji Technology Co ltd
Original Assignee
Nanchang Wanji Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanchang Wanji Technology Co ltd filed Critical Nanchang Wanji Technology Co ltd
Priority to CN202110524493.9A priority Critical patent/CN113173927A/en
Publication of CN113173927A publication Critical patent/CN113173927A/en
Withdrawn legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/10—Spiro-condensed systems
    • C07D491/107—Spiro-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1011—Condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
    • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of photoelectric display devices, in particular to a pyridyl quinoxaline delayed luminescence derivative and a preparation method thereof. The invention provides a pyridyl quinoxaline delayed luminescence derivative, which has a structure shown as a formula (I): the invention also provides a preparation method of the pyridyl quinoxaline delayed luminescence derivative, which comprises the steps of carrying out substitution reaction on a compound shown in a formula (II) and a compound shown in a formula (V) to prepare a compound shown in a formula (I); the invention provides a pyridyl quinoxaline delayed luminescence derivative and a preparation method thereof, which solve the technical problems of difficult synthesis and low device efficiency of the conventional red TADF material.

Description

Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof
Technical Field
The invention relates to the technical field of photoelectric display devices, in particular to a pyridyl quinoxaline delayed luminescence derivative and a preparation method thereof.
Background
In recent years, due to the low efficiency of conventional fluorescent organic light emitting diodes and the high cost of phosphorescent organic light emitting diodes, scientists have been interested in developing a new generation of delayed organic electroluminescent materials based on the conversion of triplet excitons into singlet excitons, such as novel organic electroluminescent materials having a triplet-triplet delayed fluorescence effect and a thermally activated delayed fluorescence effect. Among them, TADF materials are the fastest growing. In the electroluminescent tricolor material, the molecular synthesis of the material is difficult due to the red TADF. Therefore, the number of red molecular species is relatively small, and the device efficiency is not high.
Disclosure of Invention
The invention provides a pyridyl quinoxaline delayed luminescence derivative and a preparation method thereof, which solve the technical problems of difficult synthesis and low device efficiency of the conventional red TADF material.
The invention provides a pyridyl quinoxaline delayed luminescence derivative, which has a structure shown as a formula (I):
Figure BDA0003065301000000011
wherein R is selected from C1-C20 straight chain, branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthracene and substituted or unsubstituted triazinyl.
Preferably, it has the structural formula
Figure BDA0003065301000000021
The invention also provides a preparation method of the pyridyl quinoxaline delayed luminescence derivative, which comprises the steps of carrying out substitution reaction on a compound shown in a formula (II) and a compound shown in a formula (V) to prepare a compound shown in a formula (I);
Figure BDA0003065301000000022
wherein R is selected from C1-C20 straight chain, branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthracene and substituted or unsubstituted triazinyl.
The preferred time for the substitution reaction is 6 h.
Preferably, the compound represented by the formula (II) has a structural formula:
Figure BDA0003065301000000031
preferably, the compound represented by the formula (II) is prepared by the following steps:
step 1: carrying out bromination reaction on pyrene and hydrogen bromide to prepare 1-bromopyrene;
step 2: reacting the 1-bromopyrene with 2- (dimethyl-13-oxoalkyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane to prepare 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane;
and step 3: and (2) reacting the 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane with 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile to obtain the compound shown in the formula (II).
Preferably, the compound represented by the formula (II) is prepared by the following steps:
step 1: weighing ammonium chloride and sodium methoxide, dissolving in 100ml ethanol, stirring at room temperature for 60min, adding 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile into a reaction system, and reacting at 60 ℃ overnight to obtain a compound shown in a formula (IV);
Figure BDA0003065301000000032
step 2: placing the compound shown in the formula (IV) and the compound shown in the formula (VI) into a 100ml round-bottom flask, adding 50ml sodium hydroxide, and placing the reaction system into an oil bath at 130 ℃ for reaction for 10 hours; cooling, pouring the reaction liquid into water, and filtering under reduced pressure to obtain a mixture of petroleum ether: 1-dichloromethane: and 8, performing column chromatography by using an eluent, and further recrystallizing to obtain a product, namely the compound shown in the formula (III):
Figure BDA0003065301000000041
and step 3: dissolving 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane and potassium hydroxide in 150mL of dimethyl sulfoxide, heating to 75 ℃ under the condition of nitrogen, slowly adding the compound shown as the formula (III) at the moment, and reacting for 12 h; stopping the reaction and cooling to room temperature, pouring the reaction liquid into water and extracting with dichloromethane; purifying by column chromatography, using 200-mesh and 300-mesh silica gel as a stationary phase, and using petroleum ether: dichloromethane 1:2 as eluent to obtain the product, the compound shown in the formula (II).
The invention has the following beneficial effects:
the emission wavelength of the TADF material prepared by the embodiment of the invention is 630-680nm, the color coordinates of the TADF material are displayed as red light emission, the fluorescence quantum yield of the TADF material prepared by the embodiment of the invention is more than 70%, and the optimal device performance of the TADF material is as follows: the on-off voltage is 3.5V, and the luminance is 4697cd/m2The maximum external quantum efficiency can reach 18.5%.
Drawings
FIG. 1 is a TGA curve for examples 5 and 9 of the present invention;
FIG. 2 is a PL spectrum in a 2-methyltetrahydrofuran solution of example 5 and example 9 of the present invention;
FIG. 3 is a graph of transient fluorescence decay curves for examples 5 and 9 of the present invention;
FIG. 4 is a current density-voltage-luminance curve for an electroluminescent device in an embodiment of the present invention;
FIG. 5 is a graph of external quantum efficiency versus current density for an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, which are not intended to limit the present invention in any manner. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Example 1
Pyrene (2.02g, 10mmol) was dissolved in 50ml of hydrogen peroxide, and hydrogen bromide (1.21g, 15mmol), a mixed solution of ether and methanol (volume ratio ═ 1:2) was added to the above solution, stirred at 0 ℃ for 8h, and the resulting product was recrystallized in ethanol to give the product 1-bromopyrene (2.38g, yield 85%) whose chemical reaction equation was:
Figure BDA0003065301000000051
example 2
1-bromopyrene (2.81g, 10mmol), 2- (dimethyl-13-oxoalkyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane (3.46g,20mmol), 100ml of anhydrous tetrahydrofuran and butyllithium (40mmol) were added to a 250ml three-necked flask, and after introducing argon gas for 10min, the temperature was lowered to-78 ℃ to carry out a reaction for 28 hours, and after completion of the reaction, extraction purification treatment was carried out to obtain 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (2.33g, yield 71%) as a product, the chemical reaction equation of which was:
Figure BDA0003065301000000061
example 3
Quinoxaline-6, 7-dicarbonitrile (1.8g,10mmol), liquid bromine (4.795g,30mmol) and 50mL of acetic acid were added to a 100mL three-necked round bottom flask, heated under reflux under argon atmosphere and reacted for 10h at 80 ℃. Stopping the reaction and cooling to room temperature, washing the reaction solution for 2-3 times, concentrating the reaction solution, purifying the reaction solution by a chromatographic column, wherein the silica gel is 200-300 meshes, and the eluent is petroleum ether/ethyl acetate (1:4), so as to obtain 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile (2.52g, the yield is 75%) according to the chemical reaction equation:
Figure BDA0003065301000000062
example 4
4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (3.28g,10mmol) and potassium hydroxide (1.68g,30mmol) are dissolved in 150mL of dimethyl sulfoxide and heated to 75 ℃ under nitrogen, at which time 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile (3.37g,10mmol) is slowly added and reacted for 12 h. The reaction was stopped and cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane. Purifying by column chromatography, using 300-400 mesh silica gel as a stationary phase and dichloromethane as an eluent to obtain the product 2-bromo-3- (pyridine-1-yl) quinoxaline-6, 7-dicarbonitrile (3.25g, yield 71%), wherein the chemical reaction equation is as follows:
Figure BDA0003065301000000071
example 5
To a suspension of 2-bromo-3- (pyridin-1-yl) quinoxaline-6, 7-dicarbonitrile (4.59g, 10mmol) in anhydrous THF (120mL) at-78 deg.C under a nitrogen atmosphere was added n-butyllithium (6.4mL, 12.8mmol, 2.0M in cyclohexane) dropwise. Stirring was continued for 3h, then the compound of formula (V) (5.56g, 16mmol) was added, the mixture was warmed to 40 ℃ and after stirring for 6h, the reaction was monitored by TLC, the organic compound obtained was extracted with dichloromethane, the residue obtained was dissolved in dichloromethane (50ml) and after stirring for 4 h at room temperature, the organic phase was Na2SO4And (4) extracting. The crude product obtained was subjected to silica gel column chromatography (petroleum ether: dichloromethane (1: 3) as eluent) to obtain the compound (4.86g, yield 67%) whose chemical reaction equation is:
Figure BDA0003065301000000072
example 6
Ammonium chloride (2.67g, 50mmol) and sodium methoxide (2.7g, 50mmol) are weighed and dissolved in 100ml of ethanol, after stirring for 60min at room temperature, 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile (26.96g,80mmol) is added into a reaction system and reacts overnight at the temperature of 60 ℃, after the reaction is finished, the reactant is poured into an aqueous solution of diluted hydrochloric acid, the pH value is adjusted to be neutral, then the deposit is filtered under reduced pressure, and after the obtained crude product is dried, anhydrous ethanol is recrystallized to obtain a product, namely the compound shown in the formula (IV) (14.5g, the yield is 65 percent), and the chemical reaction equation is as follows:
Figure BDA0003065301000000081
example 7
The compound represented by the formula (IV) (2.22g, 5mmol) and the compound represented by the formula (VI) (1.28g, 10mmol) were weighed out and placed in a 100ml round-bottomed flask, 50ml of sodium hydroxide was added, and the reaction system was placed in an oil bath at 130 ℃ and reacted for 10 hours. Cooling, pouring the reaction liquid into water, and filtering under reduced pressure to obtain a mixture of petroleum ether: 1-dichloromethane: column chromatography with eluent 8 and further recrystallization gave the product of the compound of formula (III) (2.2g, 79% yield), which is given by the chemical equation:
Figure BDA0003065301000000082
example 8
4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane (3.28g,10mmol)
And potassium hydroxide (1.68g,30mmol) were dissolved in 150mL of dimethyl sulfoxide, and heated to 75 ℃ under nitrogen, at which time the compound represented by the formula (III) (5.58g,10mmol) was slowly added and reacted for 12 hours. The reaction was stopped and cooled to room temperature, and the reaction solution was poured into water and extracted with dichloromethane. Purifying by column chromatography, using 200-mesh and 300-mesh silica gel as a stationary phase, and using petroleum ether: dichloromethane ═ 1:2 as an eluent gave the product, compound of formula (II) (3.25g, 71% yield), according to the chemical reaction equation:
Figure BDA0003065301000000091
example 9
To a suspension of the compound represented by the formula (II) (5.58g,10mmol) in anhydrous THF (120mL) at-78 ℃ under a nitrogen atmosphere, n-butyllithium (25mL, 50mmol, 2.0M in cyclohexane) was added dropwise. Stirring was continued for 3h, then the compound of formula (V) (8.69g, 25mmol) was added, the mixture was warmed to 40 ℃ and after stirring for 6h, the reaction was monitored by TLC, the organic compound obtained was extracted with dichloromethane, the residue obtained was dissolved in dichloromethane (50ml) and after stirring for 4 h at room temperature, the organic phase was Na2SO4And (4) extracting. The crude product obtained was subjected to silica gel column chromatography (petroleum ether: dichloromethane (1: 6) as eluent) to obtain the product (5.3g, 56% yield) according to the chemical reaction equation:
Figure BDA0003065301000000101
in conclusion, the invention uses a NETZSCHRTG 209 thermal analyzer to carry out thermal weight loss analysis (under nitrogen atmosphere and with the heating rate of 10 ℃/min). Performing PL spectrum test by using a Fluoromax-4 fluorescence spectrometer of HORIBA company; testing the fluorescence quantum yield by a HAMAMATSU C11347 fluorescence quantum tester; transient lifetime testing and delayed lifetime were determined using an EdinburghInsumentsFLS 980 spectrometer. TADF material was tested for brightness, ignition voltage, etc. using a Keithley236 instrument and calibrated with a silicon photodiode. Outside the nitrogen glove box, the electroluminescence spectra (EL) and the color coordinates CIE were determined after encapsulation of the devices with an optical analyzer of the integrating sphere IS-080, PhotoResearchPR705 type, respectively. The preparation process of the device comprises the following steps:
the preparation of the organic electroluminescent diode needs the following processes:
1) and putting the film developing frame with the ITO glass substrate in acetone, isopropanol, a washing solution and deionized water, and ultrasonically treating the possibly residual stains, such as photoresist and the like, on the surface of the ITO glass substrate by using an ultrasonic device and improving interface contact. Then drying in a vacuum oven; 2) placing the ITO in an oxygen Plasma etching instrument, continuously bombarding the ITO for 30 minutes by using O2Plasma, and completely removing possible residual organic matters on the surface of the ITO glass substrate; 3) HAT-CN was spin-coated on the ITO to a thickness of 10nm, and functions to reduce the influence of leakage current while increasing hole injection. Then drying the mixture in a vacuum oven for 12 hours at a temperature of 75 ℃;
4) in a glove box under nitrogen atmosphere, α -NPD was spin-coated on the HAT-CN layer to a thickness of about 40nm and heated at 100 ℃ for 30 minutes to remove the residual solvent. 5) And a layer of PPF-doped luminous organic film is spin-coated on the alpha-NPD layer. Heating and annealing for 20 minutes at the temperature of 80 ℃ on a heating table to remove residual solvent and improve the appearance of the luminescent layer film; 6) in the vacuum evaporation chamber, a layer of lithium fluoride (LiF) which is helpful for electron injection is firstly evaporated on the luminescent layer, and the thickness is 1.5 nm. Then, a layer of aluminum (Al) cathode is evaporated, and the thickness is 150 nm. The effective area of the device is 0.18cm2. The thickness of the organic layer was measured by a quartz crystal monitoring thickness gauge. The device is prepared by polar curing and encapsulating in ultraviolet light with epoxy resin and thin-layer glass.
In summary, fig. 1 shows TGA curves of examples 5 and 9 of the present invention, and it can be seen from fig. 1 that the temperature of thermal weight loss of the TADF material produced by the example of the present invention is about 425 ℃.
Fig. 2 shows PL spectra of example 5 and example 9 of the present invention in a 2-methyltetrahydrofuran solution, and it can be seen from fig. 2 that the TADF materials prepared by the example of the present invention have emission wavelength between 630nm and 680nm, are red light emission, and example 9 is significantly red-shifted with respect to example 5, and also show ICT characteristics of the TADF materials.
FIG. 3 is a graph showing the transient fluorescence decay curves of examples 5 and 9 of the present invention, and it can be seen that the transient fluorescence decay occurs, indicating that it has a delayed fluorescence effect. Specifically, the photophysical data of the novel TADF materials obtained in examples 5 and 9 of the present invention are shown in Table 1,
TABLE 1 photophysical data of TADF materials obtained from examples 5 and 9 of the present invention
Figure BDA0003065301000000111
As can be seen from table 1, the emission wavelengths of the TADF materials prepared in the examples of the present invention are all 630-680nm, and the color coordinates of the TADF materials are all shown as red light emission, the fluorescence quantum yields of the TADF materials prepared in the examples of the present invention are all above 70%, and the retardation lifetime is short, which indicates that the roll-off of the electroluminescence efficiency of the present invention is small.
The present invention uses ITO (120nm)/HAT-CN (10 nm)/alpha-NPD (40nm)/emitter (80nm) as the device structure, PPF/LiF (1.5nm)/Al (150nm) as the TADF material, and the compounds prepared in examples 5 and 9 as the TADF material, wherein HAT-CN and alpha-NPD respectively refer to 1,4,5,8,9, 12-hexaazatriphenylene hexacyano-nitrile and 4,4' -bis (N- (naphthalene-1-yl) -N-phenylamino) biphenyl, the current density-voltage-luminance curves of the electroluminescent device are shown in FIG. 4, the external quantum efficiency-current density curves are shown in FIG. 5, and the specific electroluminescent performance data are shown in Table 2.
TABLE 2 data on the electroluminescence properties of the TADF materials obtained in examples 5 and 9 according to the invention
Examples Von L(cd/m2) EQE(％) △EST
Example 5 4.8 4697 15.1 0.029
Example 9 3.5 984 18.4 0.023
As can be seen from FIGS. 4,5 and Table 2, TADF materials obtained in examples 5 and 9 according to the present invention have gradually increased luminance, lighting voltage and Δ E with increasing degree of reactionSTGradually decreased, wherein the TADF material obtained in example 9 has the best performance, the light-on voltage is 3.5V, and the brightness is 4697cd/m2The external quantum efficiency can reach 18.5% at most, and the external quantum efficiency is prepared by the embodiment of the inventionThe external quantum efficiency of the TADF material is more than 15%, which shows that reverse system jump of T1-S1 exists in the molecular structure, and the external quantum efficiency does not change greatly with the increase of the current efficiency in the embodiment of the invention, which shows that the electroluminescent device of the TADF material prepared by the embodiment of the invention has better 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 (7)

1. A pyridyl quinoxaline delayed luminescence derivative is characterized in that the structure is shown as formula (I):
Figure FDA0003065300990000011
wherein R is selected from C1-C20 straight chain, branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthracene and substituted or unsubstituted triazinyl.
2. The pyridyl quinoxaline delayed luminescence derivative according to claim 1, having a structural formula
Figure FDA0003065300990000012
3. A preparation method of pyridyl quinoxaline delayed luminescence derivatives is characterized in that a compound shown in a formula (II) and a compound shown in a formula (V) are subjected to substitution reaction to prepare a compound shown in a formula (I);
Figure FDA0003065300990000021
wherein R is selected from C1-C20 straight chain, branched chain alkyl, substituted or unsubstituted phenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthracene and substituted or unsubstituted triazinyl.
4. The method for preparing pyridylquinoxaline delayed luminescence derivatives according to claim 3, wherein the time of the substitution reaction is 6 hours.
5. The method for preparing pyridyl quinoxaline delayed luminescence derivatives according to claim 3, wherein the compound represented by the formula (II) has the structural formula:
Figure FDA0003065300990000022
6. the method for preparing pyridylquinoxaline delayed luminescence derivatives according to claim 5, wherein the compound represented by the formula (II) is prepared by the following steps:
step 1: carrying out bromination reaction on pyrene and hydrogen bromide to prepare 1-bromopyrene;
step 2: reacting the 1-bromopyrene with 2- (dimethyl-13-oxoalkyl) -4,4,5, 5-tetramethyl-1, 3, 2-dioxaborane to prepare 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane;
and step 3: and (2) reacting the 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane with 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile to obtain the compound shown in the formula (II).
7. The method for preparing pyridylquinoxaline delayed luminescence derivatives according to claim 5, wherein the compound represented by the formula (II) is prepared by the following steps:
step 1: weighing ammonium chloride and sodium methoxide, dissolving in 100ml ethanol, stirring at room temperature for 60min, adding 2, 3-dibromoquinoxaline-6, 7-dicarbonitrile into a reaction system, and reacting at 60 ℃ overnight to obtain a compound shown in a formula (IV);
Figure FDA0003065300990000031
step 2: placing the compound shown in the formula (IV) and the compound shown in the formula (VI) into a 100ml round-bottom flask, adding 50ml sodium hydroxide, and placing the reaction system into an oil bath at 130 ℃ for reaction for 10 hours; cooling, pouring the reaction liquid into water, and filtering under reduced pressure to obtain a mixture of petroleum ether: 1-dichloromethane: and 8, performing column chromatography by using an eluent, and further recrystallizing to obtain a product, namely the compound shown in the formula (III):
Figure FDA0003065300990000032
and step 3: dissolving 4,4,5, 5-tetramethyl-2- (pyran-1-yl) -1,3, 2-dioxaborane and potassium hydroxide in 150mL of dimethyl sulfoxide, heating to 75 ℃ under the condition of nitrogen, slowly adding the compound shown as the formula (III) at the moment, and reacting for 12 h; stopping the reaction and cooling to room temperature, pouring the reaction liquid into water and extracting with dichloromethane; purifying by column chromatography, using 200-mesh and 300-mesh silica gel as a stationary phase, and using petroleum ether: dichloromethane 1:2 as eluent to obtain the product, the compound shown in the formula (II).
CN202110524493.9A 2021-05-13 2021-05-13 Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof Withdrawn CN113173927A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110524493.9A CN113173927A (en) 2021-05-13 2021-05-13 Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110524493.9A CN113173927A (en) 2021-05-13 2021-05-13 Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113173927A true CN113173927A (en) 2021-07-27

Family

ID=76929153

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110524493.9A Withdrawn CN113173927A (en) 2021-05-13 2021-05-13 Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113173927A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160316A (en) * 2022-08-02 2022-10-11 苏州大学 Orange red photo-thermal activation delayed fluorescent material and synthetic method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115160316A (en) * 2022-08-02 2022-10-11 苏州大学 Orange red photo-thermal activation delayed fluorescent material and synthetic method thereof
CN115160316B (en) * 2022-08-02 2024-03-19 苏州大学 Orange-red photo-thermal activation delay fluorescent material and synthesis method thereof

Similar Documents

Publication Publication Date Title
TWI611003B (en) Compounds for electronic devices
CN113121511B (en) Phenanthroimidazole electroluminescent material with circular polarization luminescence, preparation method and application thereof
TW202024045A (en) Materials for organic electroluminescent devices
CN112745342A (en) Fused heterocyclic compound and organic electroluminescent device thereof
CN110964019B (en) Compound taking 6-phenyl-6H-indolo [2,3-b ] quinoxaline as receptor and application thereof
CN113980040B (en) Boron-containing asymmetric spiro compound and application thereof in organic electroluminescent device
CN113173927A (en) Pyridyl quinoxaline delayed luminescence derivative and preparation method thereof
CN111153858B (en) Star-shaped electroluminescent material based on phenanthroimidazole unit and preparation method and application thereof
CN111848687B (en) Red light organic electroluminescent material, preparation method thereof and photoelectric device
KR100867134B1 (en) Light emitting polymer or derivatives thereof and light emitting device using same
WO2021036158A1 (en) Organic small molecule hole injection/transport material and preparation method therefor and application thereof
CN112661743B (en) Naphthothiodibenzofuran-based green light micromolecule and preparation method and application thereof
CN113214277A (en) Pyrenyl thiophene derivative and preparation method thereof
CN113185525A (en) Thermal activation delayed fluorescent material and preparation method thereof
CN113173926A (en) Naphtho-selenadiazole delayed fluorescent material and preparation method thereof
CN113234096A (en) Red light thermal activation delayed fluorescence material and preparation method thereof
CN113185526A (en) Green light thermal activation delayed fluorescent material and preparation method thereof
CN113185502A (en) Thioxanthone-based thermally induced delayed fluorescent material and preparation method thereof
CN113173950A (en) Phosphoric acid delayed fluorescent material and preparation method thereof
CN111909170B (en) Organic electroluminescent compound, preparation method thereof and organic electroluminescent device comprising organic electroluminescent compound
CN114075217B (en) Compound and OLED device comprising same
CN114478393B (en) Organic luminescent material with high exciton utilization rate and preparation method and application thereof
CN114805388B (en) Organic compound containing naphtho-diazole structure and preparation method and application thereof
CN114409685B (en) Organic micromolecule electroluminescent material, and preparation method and application thereof
CN112062765B (en) Organic photoelectric luminescent compound and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20210727

WW01 Invention patent application withdrawn after publication