CN111362833B - Double anthracene D-delta-A type deep blue organic fluorescent material and preparation method and application thereof - Google Patents
Double anthracene D-delta-A type deep blue organic fluorescent material and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a bianthracene D-delta-A type deep blue organic fluorescent material, a preparation method and application thereof, wherein the structural formula of the material is as follows
Wherein R is 1 R is a group with electron donating property 2 R is an electron withdrawing group 3 Is an electron donating property group or an electron withdrawing property group. The material uses the super conjugated delta bridge chain as the center to connect two anthracene light-emitting units (one with an electron-supplying characteristic group and one with an electron-withdrawing characteristic group) so as to regulate the conjugated morphology and the intramolecular charge transfer path of material molecules, so as to realize the injection balance of carriers in OLED device application, and simultaneously, further introduces the electron-donating characteristic group or the electron-withdrawing characteristic group at the para position of the center super conjugated delta bridge chain so as to effectively inhibit pi-pi stacking among material molecules, realize the high light-emitting quantum efficiency of the material molecules, and the prepared deep blue organic fluorescent material has very small efficiency roll-off,has good thermal stability and high luminescence quantum.
Description
[ field of technology ]
The invention relates to the field of organic electroluminescent diodes, in particular to a bianthracene D-delta-A type deep blue organic fluorescent material, a preparation method and application thereof.
[ background Art ]
Organic Light Emitting Diodes (OLEDs) are receiving increasing attention from the display industry due to their advantages of self-luminescence, high efficiency, wide viewing angle, high color saturation, short response time, simple manufacturing process, etc. Among OELD devices of various colors, red, green, and blue (RGB) OLED devices, which are three primary colors, are more important. Today, red and green devices have met commercial requirements, both in terms of stability and device efficiency. However, for the blue light device, as the energy gap of the blue light material is wider, the functional material matched with the blue light material is difficult to find, and the problem of device stability and efficiency roll-off is more serious than that of the red light device and the green light device, the optimization of the blue light OLED device has great significance for realizing full-color OLED display.
Commercial production has been gradually realized in recent years, and the method has been widely applied to small-area flat panel display terminals, but in order to meet the requirements of large-scale popularization and application, the performance of the device needs to be further improved, so that an OLEDs device with higher performance and lower cost is prepared, and the device is widely applied to large-area display terminals to meet the requirement of large-scale marketization. The important factors currently limiting the OLED not being fully commercialized are mainly the following: firstly, the problem of efficiency roll-off of blue light material devices is that the efficiency roll-off of blue light devices is far higher than red light and green light in commerce; secondly, the cost problem is that the blue light material has wider energy gap, so that the matched functional material is not easy to find, the undoped material is difficult to realize in vacuum evaporation, and the manufacturing cost is increased; thirdly, the service life of the blue phosphorescent material is a problem, the phosphorescent material has high luminous efficiency, but the phosphorescent material generally needs heavy metal coordination, is difficult to synthesize, has high cost and has poor service life, and especially the defects of the blue phosphorescent material are not solved. Compared with the blue phosphorescent material, the blue fluorescent material does not need expensive heavy metal coordination, has simple synthesis, low cost and long service life, and has better commercial application prospect when being used for replacing the blue phosphorescent material to prepare the OLED.
Two blue organic fluorescent materials, such as CN109265310a and CN109678759a, have been studied before in this subject group, but the efficiency roll-off of both material devices is very large and the stability is poor.
Therefore, the development of efficient and stable organic blue fluorescent materials has more realistic significance for promoting the commercialization process of the OLED.
[ invention ]
The invention aims to overcome the defects of the prior art and provide a dianthracene D-delta-A type deep blue organic fluorescent material, a preparation method and application thereof, wherein the efficiency roll-off of the prepared material is greatly reduced.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a dianthracene-based D-delta-a type deep blue organic fluorescent material, which has a chemical structural formula as follows:
wherein R is 1 R is a group with electron donating property 2 R is an electron withdrawing group 3 Is an electron donating property group or an electron withdrawing property group.
Preferably, the electron donating property group is CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Electron withdrawing group H, F, CF 3 CN or CHO.
A preparation method of a dianthracene D-delta-A type deep blue organic fluorescent material comprises the following steps: suzuki coupling reaction is carried out on the substance 7a and 9- (4-electricity-absorbing substituted phenyl) -10 borate anthracene to obtain the deep blue organic fluorescent material, wherein the substance 7a is 4- [10- (4-electricity-supplying substituted) benzanthracene ]-2,2- (4-bromophenyl) substituent propane; the 2,2- (4-bromophenyl) substituent propane in the substance 7a is 2,2- (4-bromophenyl) methylpropane, 2- (4-bromophenyl) methoxypropane, 2- (4-bromophenyl) ethylpropane, 2- (4-bromophenyl) ethoxypropane 2,2- (4-bromophenyl) t-butylpropane, 2- (4-bromophenyl) hydropropane, 2- (4-bromophenyl) fluoropropane, 2- (4-bromophenyl) trifluoropropane, 2- (4-bromophenyl)Group) cyanopropane and 2,2- (4-bromophenyl) aldehyde propane; the electricity-absorbing substituent in the 9-borate-10- (4-electricity-absorbing substituted) benzanthracene is any one of electron-absorbing characteristic groups, and the electron-absorbing characteristic groups are H, F, CF 3 CN or CHO.
Preferably, the substance 7a is obtained by Suzuki coupling reaction of 9- (4-power supply substituted phenyl) -10 borate anthracene, and the specific steps include: the 9- (4-power supply substituted phenyl) -10 borate anthracene, 2-bis (4-bromophenyl) substituent propane, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (1-3) mmol: (1-3) mmol: (0.1 to 0.3) mmol: (40-120) mL: (20-60) mL: (20-60) mmol, and purifying to obtain a substance 7a after reacting for 8-12 hours at 80-100 ℃ under the inert gas atmosphere condition; the power supply substituent in the 9- (4-power supply substituted phenyl) -10 borate anthracene is any one of power supply characteristic groups, and the power supply characteristic groups are CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 。
Further, the 9- (4-power supply substituted phenyl) -10 borate anthracene is obtained by boric acid esterification of 9-bromo-10- (4-power supply substituted) benzanthracene, and the specific steps comprise: 9-bromo-10- (4-power supply substituted) benzanthracene, isopropoxycarbonate, n-butyllithium and THF are mixed according to the following ratio (4.22-12.66) mmol: (6.32-18.96) mmol: (7.2-21.6) mmol: (50-150) mL, reacting at room temperature under the inert gas atmosphere, and purifying after the reaction is finished to obtain 9- (4-power supply substituted phenyl) -10 borate anthracene;
the 2, 2-bis (4-bromophenyl) substituent propane is obtained by brominating 2, 2-bis (4-aminophenyl) substituent propane, and the preparation method comprises the following specific steps: 2, 2-bis (4-aminophenyl) substituent propane, cuprous bromide, sodium nitrite and hydrobromic acid are mixed according to (3-10) mmol: (25-60) mmol: (10-30) mmol: (9-35) mL, and purifying to obtain 2, 2-bis (4-bromophenyl) substituent propane after reacting for 2-4 hours at room temperature under the inert gas atmosphere condition.
Further, the 9-bromo-10- (4-power supply substituted) benzanthracene is obtained by brominating 9- (4-power supply substituted) benzanthracene, and the specific steps comprise: 9- (4-power supply substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are mixed according to (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the inert gas atmosphere condition, and purifying to obtain 9-bromo-10- (4-power supply substituted) benzanthracene;
The 9- (4-power supply substituted) benzanthracene is 9-bromoanthracene which is obtained through Suzuki coupling reaction, and the specific preparation steps comprise: 9-bromoanthracene, 4-power supply substituted phenylboronic acid, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL: (50-200) mmol, and reacting for 12-24 hours at 100-110 ℃ under the inert gas atmosphere condition, and purifying to obtain 9- (4-power supply substituted) benzanthracene.
Preferably, the 9- (4-electroabsorption substituted phenyl) -10 borate anthracene is obtained by boric acid esterification of 9-bromo-10- (4-electroabsorption substituted) benzanthracene, and the specific steps comprise: 9-bromo-10- (4-electro-absorption substituted) benzanthracene, isopropoxycarbonate, n-butyllithium and THF are mixed according to the following ratio (4.22-12.66) mmol: (6.32-18.96) mmol: (7.2-21.6) mmol: (50-150) mL, reacting at room temperature under the inert gas atmosphere, and purifying after the reaction is finished to obtain 9- (4-electricity-absorbing substituted phenyl) -10-borate anthracene.
Further, the 9-bromo-10- (4-electro-absorption substituted) benzanthracene is obtained by brominating 9- (4-electro-absorption substituted) benzanthracene, and the specific steps comprise: 9- (4-electroabsorption substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are mixed according to (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the inert gas atmosphere condition, and purifying to obtain 9-bromo-10- (4-electricity-absorbing substituted) benzanthracene;
The 9- (4-electro-absorption substituted) benzanthracene is 9-bromoanthracene which is obtained by Suzuki coupling reaction, and the specific preparation steps comprise: 9-bromoanthracene, 4-electroabsorption substituent phenylboronic acid, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL: (50-200) mmol, and reacting for 12-24 hours at 100-110 ℃ under the inert gas atmosphere condition, and purifying to obtain 9- (4-electricity-absorbing substituted) benzanthracene.
Preferably, the Suzuki coupling reactionA catalyst, a solvent and an activator are also added; wherein the ratio of the substances 7a, 9- (4-electroabsorption substituted phenyl) -10 borate anthracene, the catalyst, the solvent and the activator is (0.25-1) mmol: (0.21-0.84) mmol: (0.03-0.12) mmol: (25-100) mL: (8.4-33.6) mmol; the catalyst adopts tetra (triphenylphosphine) palladium; the solvent adopts a mixed solvent of toluene and homogeneous solvent ethanol; k is used as activator 2 CO 3 A solution;
the Suzuki coupling reaction is carried out for 12-24 hours at the temperature of 100-110 ℃ under the atmosphere of nitrogen gas.
The application of the dianthracene D-delta-A type deep blue organic fluorescent material in the organic electroluminescent diode fitting.
Compared with the prior art, the invention has the following beneficial effects:
The invention discloses a dianthracene D-delta-A type deep blue organic fluorescent material which is an anthracene derivative and can realize blue light emission. The invention adopts a central super-conjugated delta bridge chain to connect two anthracene light-emitting units (one with an electron-donating characteristic group and one with an electron-withdrawing characteristic group), regulates and controls the intramolecular charge transfer characteristic through the two DA units, and simultaneously realizes the balance of carrier injection in OLED device application. On the other hand, the prior deep blue light material basically adopts fully conjugated benzene rings as bridge chains to connect two light-emitting units, and because adjacent C atom orbitals on the benzene rings adopt Sp 2 Hybridization, resulting in tighter pi-pi stacking between organic molecules, the C atom orbitals of the super-conjugated delta-bridge chain of the invention adopts Sp 3 Hybridization can weaken fluorescence quenching caused by pi-pi accumulation among organic molecules. By introducing a sterically hindered group, i.e. a group having electron donating or electron withdrawing properties, on the central super-conjugated delta bridge chain, pi-pi stacking between organic molecules is further inhibited, eliminating stacked interactions between organic material molecules. In an undoped OLED device, blue light emission is realized, and the performance is good. In summary, the invention is characterized in that: 1) The super conjugated delta bridge chain is adopted to connect two anthracene light-emitting units, so that the conjugated morphology and excited state charge transfer of organic molecules and charge injection leveling in OLED device application are realized Regulating and controlling the balance; 2) The central super conjugated bridge chain is introduced with a group with electron-donating property or a group with electron-withdrawing property to inhibit pi-pi interaction between organic molecules, so that the efficiency roll-off of the device is greatly reduced, and the stability is improved.
The invention also discloses a preparation method of the double anthracene D-delta-A type deep blue organic fluorescent material, which uses a super-conjugated delta bridge chain to connect two (one with a group with electron-donating property and one with electron-withdrawing property) anthracene light-emitting units, so as to realize the regulation and control of the conjugated morphology and the excited state charge transfer path of organic molecules, further realize the injection balance of carriers in OLED device application, and simultaneously introduce the group with electron-donating property or the group with electron-withdrawing property on the super-conjugated delta bridge chain to inhibit pi-pi interaction among organic molecules, thereby successfully preparing the deep blue organic fluorescent material with high thermal stability, high fluorescence quantum efficiency and low roll-off rate; the whole synthesis process is simple, the yield is high, the purification is easy, the manufacturing cost can be reduced, and the production process is simplified.
The invention also discloses an application of the dianthracene D-delta-A type deep blue organic fluorescent material in an organic electroluminescent diode fitting, and the deep blue organic fluorescent material can be used for successfully preparing a high-performance undoped blue OLED device; the prepared deep blue OLED device has strong deep blue fluorescence emission of the solution or the film under the irradiation of ultraviolet light. When the material is applied to undoped OLED, the efficiency roll-off is very small, the stability of the device is greatly improved, and in addition, the EQE (about 3.42%) is far higher than the theoretical calculated EQE value (about 1.95%), [ EQE Theory of ＝η eh ·η PL ·η exciton ·η out =1×0.26×0.25×0.3=1.95% >, where η eh Is the recombination rate of electrons and holes; η (eta) PL Fluorescence quantum yield eta as net film exciton The ratio of excitons; η (eta) out Is light transmittance.
[ description of the drawings ]
FIG. 1 is a nuclear magnetic resonance spectrum of a deep blue organic fluorescent material prepared in example 1 of the present invention.
FIG. 2 is a mass spectrum of a deep blue organic fluorescent material prepared in example 1 of the present invention.
FIG. 3 is a thermogravimetric diagram of a deep blue organic fluorescent material according to example 1 of the present invention.
FIG. 4 shows absorption spectra of deep blue organic fluorescent materials prepared in example 1 of the present invention in different solutions.
FIG. 5 shows the emission spectra of the deep blue organic fluorescent material prepared in example 1 of the present invention in different solutions.
FIG. 6 shows absorption and emission spectra of a deep blue organic fluorescent material prepared in example 1 of the present invention on a thin film.
FIG. 7 is an Electroluminescence (EL) pattern of the device 1 produced by the present invention.
FIG. 8 is a graph of current density versus voltage versus luminance (Cd-V-L) for device 1 made in accordance with the present invention.
Fig. 9 is a graph of current efficiency versus current density versus power efficiency (CE-Cd-PE) for device 1 made in accordance with the present invention.
FIG. 10 is a graph of current density versus external quantum efficiency (Cd-EQE) for device 1 made in accordance with the present invention.
[ detailed description ] of the invention
The invention is described in further detail below with reference to specific steps and figures:
the invention discloses a bianthracene D-delta-A type deep blue organic fluorescent material, a preparation method and application thereof; according to the invention, through precise design of material molecules, wherein a super-conjugated delta bridge chain is used for connecting two anthracene molecule light-emitting units, so that the conjugated morphology and an excited state charge transfer path of organic molecules are regulated and controlled, the charge injection balance in the application of an OLED device is realized, meanwhile, steric hindrance groups are introduced at two ends of a central super-conjugated delta bridge chain to inhibit pi-pi stacking action between the organic molecules, and the prepared deep blue organic fluorescent material has good thermal stability, high light-emitting quantum efficiency and low roll-off rate. The chemical structural formula is as follows.
Wherein the method comprises the steps of，R 1 R is a group of electron donating nature 2 A group of electron withdrawing character, R 3 The group of electron donating property is preferably CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The electron withdrawing group is preferably H, F, CF 3 CN or CHO; the chemical structural formula of the synthesized deep blue organic fluorescent material is exemplified as follows:
sequentially a compound a, a compound b, a compound c, a compound d, a compound e, a compound f, a compound g, a compound h, a compound i, a compound j, a compound m and a compound n;
| R 1 | CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 |
| R 2 | H、F、CF 3 CN or CHO |
| R 3 | CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 、C(CH 3 ) 3 、H、F、CF 3 CN or CHO |
Wherein the compound is R 1 、R 2 、R 3 The above chemical formulas are only partially exemplified as any one of the combinations of the above.
The specific synthetic route of the deep blue organic fluorescent material is shown in the following formula (1):
2a in the above formula denotes
3a denotes->
4a denotes +.>
Corresponding 2b denotes +.>
3b denotes->
4b indicates->
Taking the synthesis of the compound a as an example, a specific synthesis route is shown in the following formula (2):
the specific process of the material synthesis process comprises the following steps:
step 1, synthesizing a group with electronic characteristics
(1) 9-Bromoanthracene 57.5 to 30mmol of 4-powered substituted phenylboronic acid (2 a), 15 to 60mL of potassium carbonate solution, 50 to 200mL of toluene and 15 to 60mL of ethanol are added into a reaction bottle, wherein the potassium carbonate solution is prepared by adding 50 to 200mmol of potassium carbonate solid into 15 to 60mL of water; finally, 0.25 to 1mmol of tetra (triphenylphosphine) palladium is added. Then the system is vacuumized, and the reflux is carried out for 12 to 24 hours at the temperature of 100 to 110 ℃ under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain 9- (4-power supply substituted) benzanthracene (3 a); wherein the electron donating substitution is any one of the groups of electron donating character, including CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 And C (CH) 3 ) 3 。
(2) Bromination of 9- (4-powered substituted) benzanthracene: 2.50 to 10mmol of 9- (4-power supply substituted) benzanthracene, 40 to 150mL of N, N-Dimethylformamide (DMF) and 3 to 12mmol of N-bromosuccinimide (NBS) are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 1 to 2 hours at the temperature of 85 to 90 ℃ under the protection of nitrogen, the reaction product is washed by methanol, and the 9-bromo-10- (4-power supply substituted) benzanthracene (4 a) is obtained by suction filtration.
(3) Boration of 9-bromo-10- (4-electron donating substituted) benzanthracene: 4.22-12.66 mmol of 9-bromo-10- (4-power supply substituted) benzanthracene (4 a), 6.32-18.96 mmol of isopropoxycarbonate, 7.2-21.6 mmol of n-butyllithium (added at-78 ℃) and 50-150 mL of THF are added into a reaction bottle, then the system is vacuumized and stirred for 8-12 hours at room temperature under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-power supply substituted phenyl) -10 boric acid ester anthracene (5 a).
(1) Adding 5-20 mmol of 9-bromoanthracene, 7.5-30 mmol of 4-electricity-absorbing substituent phenylboronic acid (2 b), 15-60 mL of potassium carbonate solution, 50-200 mL of toluene and 15-60 mL of ethanol into a reaction bottle, wherein the potassium carbonate solution is prepared by adding 50-200 mmol of potassium carbonate solid into 15-60 mL of water; finally, 0.25 to 1mmol of tetra (triphenylphosphine) palladium is added. Then the system is vacuumized, and the reflux is carried out for 12 to 24 hours at the temperature of 100 to 110 ℃ under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain 9- (4-absorption)Electrically substituted) benzanthracene (3 b); wherein the electron withdrawing substitution is any one of groups with electron withdrawing property, including H, F, CF 3 、CN、CHO。
(2) Bromination of 9- (4-electroabsorption substituted) benzanthracene: 2.50-10 mmol of 9- (4-electroabsorption substituted) benzanthracene (3 b), 40-150 mL of N, N-Dimethylformamide (DMF) and 3-12 mmol of N-bromosuccinimide (NBS) are added into a reaction bottle, then the reaction bottle is vacuumized, the reaction product is washed by methanol after the reaction is reacted for 1-2 hours at 85-90 ℃ under the protection of nitrogen, and the 9-bromo-10- (4-electroabsorption substituted) benzanthracene (4 b) is obtained by suction filtration.
(3) Boration of 9-bromo-10- (4-electroabsorption substituted) benzanthracene: 4.22 to 12.66mmol of 9-bromo-10- (4-electroabsorption substituted) benzanthracene (4 b) prepared in the step 1, 6.32 to 18.96mmol of isopropoxycarbonate, 7.2 to 21.6mmol of n-butyllithium (added at the temperature of minus 78 ℃), 50 to 150mL of THF (tetrahydrofuran) are added into a reaction bottle, and then the system is vacuumized and stirred for 8 to 12 hours at room temperature under the protection of nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-electricity-absorbing substituted phenyl) -10 borate anthracene (5 b).
(1) Bromination of 2, 2-bis (4-aminophenyl) substituent propane: 3-10 mmol of 2, 2-bis (4-aminophenyl) substituent propane, 25-60 mmol of cuprous bromide (prepared by dissolving 18-70 mL of hydrobromic acid), 12-30 mmol of sodium nitrite (prepared by dissolving 10-30 mL of distilled water) and 9-35 mL of hydrobromic acid are added into a reaction bottle, then the reaction bottle is vacuumized, the reaction is carried out for 1.5-3 hours at room temperature under the protection of nitrogen, and after the reaction is finished, the 2, 2-bis (4-bromophenyl) substituent propane (6 a) is obtained through extraction, rotary evaporation, column chromatography and recrystallization.
(2) Suzuki coupling of 9- (4-electron-donating substituted phenyl) -10 boronate anthracene: 1 to 3mmol of 9- (4-power supply substituted phenyl) -10 borate anthracene (5 a), 1 to 3mmol of 2, 2-bis (4-bromophenyl) substituent propane (6 a), 0.1 to 0.3mmol of tetra (triphenylphosphine) palladium, 40 to 120mL of toluene, 10 to 30mL of ethanol and K 2 CO 3 Adding 40-120 mL of solution (prepared by dissolving in 10-30 mL of distilled water) into a reaction bottle, vacuumizing the system, reacting for 8-12 hours at 80-100 ℃ under the protection of nitrogen, and extracting after the reaction is finishedSpin-steaming, column chromatography, and recrystallizing to obtain 4- [10- (4-power supply substituted) benzanthracene]-2,2- (4-bromophenyl) substituent propane (7 a); the substituent group in the 2,2- (4-bromophenyl) substituent propane is R 3 ，R 3 Any of the electron donating property groups or any of the electron withdrawing property groups can be any of the electron donating property groups including CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 And C (CH) 3 ) 3 In (a) and (b); the electron withdrawing group includes H, F, CF 3 CN and CHO.
(3) Synthesis of the final product: 7a of substance 0.25-1 mmol, 5b of the product obtained in the step 2, namely 0.21-0.84 mmol of 9- (4-electricity-absorbing substituted phenyl) -10 borate anthracene, 0.03-0.12 mmol of catalyst tetra (triphenylphosphine) palladium, 15-60 mL of toluene, 5-20 mL of ethanol and K 2 CO 3 8.4-33.6 mmol (prepared into solution by 5-20 mL distilled water), and reflux for 12-24 h at 100-110 ℃ under the protection of nitrogen. After the reaction is finished, methanol is subjected to hot washing, suction filtration, toluene recrystallization and sublimation to obtain a final product, namely the organic blue fluorescent material.
The potassium carbonate solution is added to activate the borate ion and convert it to the reactive intermediate. Ethanol is added to increase the hydrophilicity of the solvent, allowing the reaction to proceed under homogeneous conditions.
Intermediate A in the examples below 1 ～A 10 The representation factor R 3 The groups are different and the intermediates synthesized are different.
Example 1
Step 1, synthesizing a power supply characteristic group: (1) to the reaction flask was added 5mmol of 9-bromoanthracene, 7.5mmol of 4-methoxyphenylboronic acid, 50mmol of potassium carbonate solution (prepared as a solution with 15mL of distilled water), 50mL of toluene, 15mL of ethanol, and finally 0.25mmol of tetrakis (triphenylphosphine) palladium. Then the system is vacuumized and refluxed for 12 hours at 100 ℃ under the protection of nitrogen. After the reaction, the mixture is extracted, distilled, subjected to column chromatography (eluent: n-hexane/dichloromethane=4:1) and recrystallized to obtain 9- (4-methoxy) benzanthracene. The yield was 86%. (2) 2.50mmol of 9- (4-methoxy) benzanthracene, 40mL of N, N-Dimethylformamide (DMF) and 3mmol of N-bromosuccinimide (NBS) were added to the reaction flask, and the system was evacuated and reacted at 85℃for 1 hour under nitrogen protection. Washing with methanol, and suction filtering to obtain the product. The yield was 88%. (3) 9-bromo-10- (4-methoxy) benzanthracene 4.22mmol, isopropoxycarbonate 6.32mmol, n-butyllithium 7.2mmol (added at-78 ℃ C.) and THF 50mL were added to the reaction flask, and the system was then evacuated and stirred at room temperature for 8 hours under nitrogen. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-methoxy) -10-borate anthracene. The yield was 78%.
Example 2
Step 1, synthesizing a power supply characteristic group: (1) 10mmol of 9-bromoanthracene, 15mmol of 4-methoxyphenylboronic acid, 100mmol of potassium carbonate solution (prepared as a solution by 30mL of distilled water), 100mL of toluene, 30mL of ethanol are added to a reaction flask, and finally 0.5mmol of tetrakis (triphenylphosphine) palladium is added. Then the system is vacuumized and refluxed for 18 hours at 110 ℃ under the protection of nitrogen. After the reaction, the mixture is extracted, distilled, subjected to column chromatography (eluent: n-hexane/dichloromethane=4:1) and recrystallized to obtain 9- (4-methoxy) benzanthracene. The yield was 88%. (2) 5mmol of 9- (4-methoxy) benzanthracene, 80mL of N, N-Dimethylformamide (DMF) and 6mmol of N-bromosuccinimide (NBS) were added to the reaction flask, and the system was evacuated and reacted at 85℃for 1.5 hours under nitrogen protection. Washing with methanol, and suction filtering to obtain the product. The yield was 90%. (3) 9-bromo-10- (4-methoxy) benzanthracene 8.44mmol, isopropoxycarbonate 12.64mmol, n-butyllithium 14.4mmol (added at-78 ℃ C.) and THF 100mL were added to the reaction flask, and the system was evacuated and stirred at room temperature for 10 hours under nitrogen protection. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-methoxy) -10-borate anthracene. The yield was 80%.
Example 3
Step 1, synthesizing a power supply characteristic group: (1) 20mmol of 9-bromoanthracene, 30mmol of 4-methoxyphenylboronic acid, 200mmol of potassium carbonate solution (prepared as a solution with 60mL of distilled water), 200mL of toluene, 60mL of ethanol are added to a reaction flask, and finally 1mmol of tetrakis (triphenylphosphine) palladium is added. Then the system is vacuumized and refluxed for 20 hours at 110 ℃ under the protection of nitrogen. After the reaction, the mixture is extracted, distilled, subjected to column chromatography (eluent: n-hexane/dichloromethane=4:1) and recrystallized to obtain 9- (4-methoxy) benzanthracene. The yield was 90%. (2) 10mmol of 9- (4-methoxy) benzanthracene, 160mL of N, N-Dimethylformamide (DMF) and 12mmol of N-bromosuccinimide (NBS) are added into a reaction bottle, and then the system is vacuumized and reacted for 1.5 hours at 90 ℃ under the protection of nitrogen. Washing with methanol, and suction filtering to obtain the product. The yield was 92%. (3) 9-bromo-10- (4-methoxy) benzanthracene 16.88mmol, isopropoxycarbonate 25.28mmol, n-butyllithium 28.8mmol (added at-78 ℃ C.) and THF 200mL were added to the reaction flask, the system was then evacuated and stirred at room temperature for 12 hours under nitrogen protection. After the reaction is finished, extracting, rotary steaming, column chromatography and recrystallization are carried out to obtain the product 9- (4-methoxy) -10-borate anthracene. The yield thereof was found to be 82%.
Example 4
Step (a)3, synthesizing a final product: (1) 3mmol of 2, 2-bis (4-aminophenyl) hydrogen propane, 25mmol of cuprous bromide (prepared by dissolving in 9mL of hydrobromic acid), 12mmol of sodium nitrite (prepared by dissolving in 5mL of distilled water) and 9mL of hydrobromic acid are added into a reaction bottle, then the system is vacuumized, the reaction is carried out for 1.5 hours at room temperature under the protection of nitrogen, after the reaction is finished, the extraction, rotary steaming and column chromatography are carried out, and the product 2, 2-bis (4-bromophenyl) hydrogen propane is obtained by recrystallization. The yield was 90%. (2) The product obtained in step 1, i.e., 1mmol of 9- (4-methoxy) -10-borate anthracene, 1mmol of 2, 2-bis (4-bromophenyl) hydrogen propane, 0.1mmol of tetrakis (triphenylphosphine) palladium, 40mL of toluene, 10mL of ethanol and K 2 CO 3 40mmol (prepared into solution by 10mL distilled water) is added into a reaction bottle, then the system is vacuumized, nitrogen is protected, the reaction is carried out for 8 hours at 80 ℃, after the reaction is finished, the extraction, rotary evaporation and column chromatography (eluent: n-hexane/dichloromethane=4:1) are carried out, and the product A is obtained by recrystallization 2 . The yield was 48%. (3) Will A 2 0.25mmol, the product obtained in step 2, namely 0.30mmol of 9- (4-cyanophenyl) -10-borate anthracene, 0.03mmol of catalyst tetra (triphenylphosphine) palladium, 15mL of toluene, 5mL of ethanol, K 2 CO 3 8.4mmol (prepared as a solution in 5mL of distilled water) was added to the flask and refluxed at 110℃for 12h under nitrogen. After the reaction, extraction, rotary evaporation and column chromatography (eluent: n-hexane/dichloromethane=3:1) are carried out, and the final product b is obtained through recrystallization. The yield was 86%. Molecular formula C 55 H 37 NO, theoretical 727.89 and actual 727.
Example 5
Step (1), step (2) and step (3) are the same as in example 2.
Example 6
Step (3) in steps 1, 2 and step 3 is the same as in example 3.
Example 7
Example 8
Example 9
Example 10
Example 11
Example 12
Example 13
As in example 1. (only the 4-methoxy phenylboronic acid and the 4-methyl cyanophenylboronic acid in the step (1) of the steps 1 and 2 are replaced by 4-methyl phenylboronic acid and 4-fluoro phenylboronic acid respectively, and the 2, 2-bis (4-aminophenyl) trifluoromethyl propane in the step (1) is replaced by 2, 2-bis (4-aminophenyl) hydropropane, so that the corresponding functional groups in the following steps are replaced correspondingly) to prepare the product k.
Example 14
As in example 1. (only the 4-methoxy phenylboronic acid and the 4-methyl cyanophenylboronic acid in the step (1) of the steps 1 and 2 are respectively replaced by 4-ethyl phenylboronic acid and 4-trifluoromethyl phenylboronic acid, and the corresponding functional groups in the following steps are correspondingly replaced) to prepare the product I.
Example 15
As in example 1. (only the 4-methoxyphenylboronic acid and the 4-methoxyphenylboronic acid in the step (1) of the steps 1 and 2 are replaced by the 4-ethoxyphenylboronic acid and the phenylboronic acid respectively, and the 2, 2-bis (4-aminophenyl) trifluoromethyl propane in the step (1) is replaced by the 2, 2-bis (4-aminophenyl) hydropropane, so that the functional groups required to be replaced in the following steps are correspondingly replaced) to obtain the product m.
Example 16
As in example 1. (only the 4-methoxyphenylboronic acid and the 4-methoxyphenylboronic acid in the step (1) of the steps 1 and 2 are replaced by the 4-tert-butylphenylboronic acid and the 4-aldehyde phenylboronic acid respectively, and the functional groups required to be replaced in the following steps are correspondingly replaced) to prepare the product n.
The thermal weight spectrum of the target product a in the above example 1 is shown in fig. 3, and the thermal decomposition temperature of a can be obtained from the thermal weight spectrum to be 400 ℃, which indicates that the compound a has good thermal stability.
The target product a of example 1 above was tested in cyclohexane, toluene and 1, 2-dichloroethane solution (-10), respectively -6 mol L -1 ) And ultraviolet absorption and fluorescence emission spectra on the film, and the deep blue organic fluorescent materials prepared in example 1 of fig. 4 and 5 are absorption and emission spectra in different solutions, respectively; fig. 6 is an absorption (circular) and emission (square) spectrum of the deep blue organic fluorescent material prepared in example 1 in a thin film: as can be seen from FIG. 4, the absorption peaks of compound a in different solvents are 355/373/393, 355/377/397, 356/378/398nm, respectively, which are characteristic absorption peaks derived from anthracene. The polarity of the solvent is not changed greatly from small to large, which means that the dipole moment of the ground state of the molecule is changed little. As can be seen from FIG. 5, the emission peaks of material a in different solvents are 4 respectively16. 421, 424nm, in which there is a red shift with increasing polarity of the solvent and the shoulder gradually decreases due to the change in dipole moment within the molecule in the excited state. As can be seen from fig. 6, the absorption peaks of compound a are 360, 379, 400, respectively, and the emission peak is 441nm, which are characteristic absorption and emission peaks derived from anthracene.
Application example 1
Preparation of organic electroluminescent device 1
The organic electroluminescent device 1 was prepared according to the following method:
a) Cleaning ITO (indium tin oxide) glass: ultrasonically cleaning ITO glass by using solvents such as detergent, deionized water, acetone and isopropanol for 10 minutes respectively, and then treating in a plasma cleaner for 10 minutes, wherein the sheet resistance is 15-20 ohm/sq;
b) Vacuum evaporating a hole injection layer HAT-CN on anode ITO glass, wherein the thickness is 15nm;
c) Vacuum evaporating a hole transport layer TAPC on the hole injection layer HAT-CN, wherein the thickness is 60nm;
d) Vacuum evaporating an electron blocking layer TCTA on the hole transport layer TAPC, wherein the thickness of the electron blocking layer TCTA is 10nm;
e) Vacuum evaporating a luminescent layer compound a on the electron blocking layer TCTA, wherein the thickness is 20nm;
f) Vacuum evaporating TPBi as an electron transport layer on the light-emitting layer, wherein the thickness of the TPBi is 40nm;
g) Vacuum evaporating an electron injection layer LiF on the electron transport layer, wherein the thickness of the electron injection layer LiF is 1nm;
h) And vacuum evaporating cathode Al on the electron injection layer, wherein the thickness of the cathode Al is 100nm.
The structure of the organic electroluminescent device 1 is ITO (110 nm)/HAT-CN (15 nm)/TAPC (60 nm)/TCTA (10 nm)/EML [ a (20 nm) ]/TPBi (40 nm)/LiF (1 nm)/Al (100 nm) which are laminated in sequence.
The molecular structural formula of the material used in the device 1 (the light-emitting layer is the compound a) is shown in the following table 1.
Table 1 molecular structure of materials used for device 1
The light Emission (EL) spectrum, current density-voltage-luminance (Cd-V-L) spectrum, current density-current efficiency (Cd-CE-PE), and current density-external quantum efficiency (Cd-EQE) of the device 1 were tested as shown in fig. 7, 8, 9, and 10, respectively: from fig. 7, it can be derived that: the device 1 is the luminescence from compound a, as can be derived from fig. 8: the maximum current efficiency of device 1 is 3.64Cd/A. From fig. 9 and 10, it follows that: the efficiency roll-off of the device 1 is very small, which indicates that the device has good efficiency stability; it can be seen that the efficiency roll-off of the devices made of the materials of the present invention is greatly reduced, i.e., the stability is greatly improved, compared to the efficiency roll-off of the devices made of the materials of CN109265310a and CN109678759 a.
The parameters of the photovoltaic performance of device 1 are shown in table 2 below.
Table 2 optoelectronic parameters of electroluminescent device 1
In the above table, a 'device name, b' light emitting layer, c 'represents lighting voltage, d' represents maximum current efficiency, e 'represents maximum power efficiency, f' represents maximum external quantum efficiency, g 'represents maximum external quantum efficiency at 500cd/a, and h' represents color purity Coordinates (CIE).
The lighting voltage of the organic device based on the material is 3.8V, and the undoped deep blue OLED device driven by low voltage is realized. The organic light-emitting device of the present invention can be used in light sources such as electrophotographic photoreceptors, flat panel displays, copiers, printers, liquid crystal display backlights, timers, various light-emitting devices, various display devices, various signs, various sensors, various house plates, and the like.
The material prepared by the invention has the characteristics of low synthesis cost, high yield, easy purification and the like, and shows strong deep blue fluorescence emission in a solution or film state. The material prepared by the invention is applied to OLED devices, realizes deep blue light emission, has a maximum EQE of 3.42%, and has very small efficiency roll-off. The material prepared by the invention has certain application value and market prospect in the organic photoelectric fields of organic display, organic solid-state lighting and the like.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. A bianthracene D-delta-A type deep blue organic fluorescent material is characterized in that: the chemical structural formula of the dianthracene-based D-delta-A type deep blue organic fluorescent material is as follows:
wherein R is 1 R is a group with electron donating property 2 R is an electron withdrawing group 3 Is an electron donating property group or an electron withdrawing property group;
the electron donating property group is CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Electron withdrawing group F, CF 3 CN or CHO.
2. A method for preparing the dianthracene D-delta-a type deep blue organic fluorescent material according to claim 1, which is characterized in that: the method comprises the following steps: suzuki coupling reaction is carried out on the substance 7a and 9- (4-electricity-absorbing substituted phenyl) -10 borate anthracene to obtain the deep blue organic fluorescent material, wherein the substance 7a is 4- [10- (4-electricity-supplying substituted) benzanthracene ]-2,2- (4-bromophenyl) substituent propane; the electron-withdrawing substituent in the 9- (4-electron-withdrawing substituted phenyl) -10 borate anthracene is any one of electron-withdrawing characteristic groups, and the electron-withdrawing characteristic groups are F, CF 3 CN or CHO;
the substance 7a is obtained by carrying out Suzuki coupling reaction on 9- (4-power supply substituted phenyl) -10 borate anthracene, and the specific steps comprise: 9- (4-Power supply substituted phenyl) -10 borate anthracene, 2-bis (4-bromophenyl) substituent propane, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (1-3) mmol: (1-3) mmol: (0.1 to 0.3) mmol: (40-120) mL: (20-60) mL: (20-60) mmol, and purifying to obtain a substance 7a after reacting for 8-12 hours at 80-100 ℃ under the inert gas atmosphere condition; the power supply substituent in the 9- (4-power supply substituted phenyl) -10 borate anthracene is any one of power supply characteristic groups, and the power supply characteristic groups are CH 3 、OCH 3 、C 2 H 5 、OC 2 H 5 Or C (CH) 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the The 2, 2-bis (4-bromophenyl) substituent propane is a compound shown in a formula 6 a:
wherein R3 is Me, OMe, et, OEt, tBu, H, F, CF 3 CN or CHO, and the two R3 in formula 6a are the same.
3. The method for preparing the dianthracene D-delta-A type deep blue organic fluorescent material according to claim 2, which is characterized in that: the 9- (4-power supply substituted phenyl) -10 borate anthracene is obtained by esterification of 9-bromo-10- (4-power supply substituted) benzanthracene boric acid, and the specific steps comprise: 9-bromo-10- (4-power supply substituted) benzanthracene, isopropoxycarbonate, n-butyllithium and THF are mixed according to the following ratio (4.22-12.66) mmol: (6.32-18.96) mmol: (7.2-21.6) mmol: (50-150) mL, reacting at room temperature under the inert gas atmosphere, and purifying after the reaction is finished to obtain 9- (4-power supply substituted phenyl) -10 borate anthracene;
The 2, 2-bis (4-bromophenyl) substituent propane is obtained by brominating 2, 2-bis (4-aminophenyl) substituent propane, and the preparation method comprises the following specific steps: 2, 2-bis (4-aminophenyl) substituent propane, cuprous bromide, sodium nitrite and hydrobromic acid are mixed according to (3-10) mmol: (25-60) mmol: (10-30) mmol: (9-35) mL, and purifying to obtain 2, 2-bis (4-bromophenyl) substituent propane after reacting for 2-4 hours at room temperature under the inert gas atmosphere condition;
the 2, 2-bis (4-aminophenyl) substituent propane is a compound shown in a formula 6:
wherein R3 is Me, OMe, et, OEt, tBu, H, F, CF 3 CN or CHO, and the two R3 in formula 6a are the same.
4. The method for preparing a dianthracene D-delta-a type deep blue organic fluorescent material according to claim 3, wherein the method comprises the following steps: the 9-bromo-10- (4-power supply substituted) benzanthracene is obtained by brominating 9- (4-power supply substituted) benzanthracene, and the specific steps comprise: 9- (4-power supply substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are mixed according to (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the inert gas atmosphere condition, and purifying to obtain 9-bromo-10- (4-power supply substituted) benzanthracene;
The 9- (4-power supply substituted) benzanthracene is 9-bromoanthracene which is obtained through Suzuki coupling reaction, and the specific preparation steps comprise: 9-bromoanthracene, 4-power supply substituted phenylboronic acid, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL:
(50-200) mmol, and reacting for 12-24 hours at 100-110 ℃ under the inert gas atmosphere condition, and purifying to obtain 9- (4-power supply substituted) benzanthracene.
5. The method for preparing the dianthracene D-delta-A type deep blue organic fluorescent material according to claim 2, which is characterized in that: the 9- (4-electroabsorption substituted phenyl) -10 borate anthracene is obtained by boric acid esterification of 9-bromo-10- (4-electroabsorption substituted) benzanthracene, and comprises the following specific steps: 9-bromo-10- (4-electro-absorption substituted) benzanthracene, isopropoxycarbonate, n-butyllithium and THF are mixed according to the following ratio (4.22-12.66) mmol: (6.32-18.96) mmol: (7.2-21.6) mmol: (50-150) mL, reacting at room temperature under the inert gas atmosphere, and purifying after the reaction is finished to obtain 9- (4-electricity-absorbing substituted phenyl) -10-borate anthracene.
6. The method for preparing the dianthracene D-delta-A type deep blue organic fluorescent material according to claim 5, wherein the method comprises the following steps: the 9-bromo-10- (4-electroabsorption substituted) benzanthracene is obtained by brominating 9- (4-electroabsorption substituted) benzanthracene, and comprises the following specific steps: 9- (4-electroabsorption substituted) benzanthracene, N-bromosuccinimide and N, N-dimethylformamide are mixed according to (2.5-10) mmol: (3-12) mmol: (40-150) mL, reacting for 1-2 hours at 85-90 ℃ under the inert gas atmosphere condition, and purifying to obtain 9-bromo-10- (4-electricity-absorbing substituted) benzanthracene;
The 9- (4-electro-absorption substituted) benzanthracene is 9-bromoanthracene which is obtained by Suzuki coupling reaction, and the specific preparation steps comprise: 9-bromoanthracene, 4-electroabsorption substituent phenylboronic acid, tetra (triphenylphosphine) palladium, toluene, ethanol and K 2 CO 3 According to (5-20) mmol: (7.5-30) mmol: (0.25-1) mmol: (50-200) mL: (15-60) mL:
(50-200) mmol, and reacting for 12-24 hours at 100-110 ℃ under the inert gas atmosphere condition, and purifying to obtain 9- (4-electricity-absorbing substituted) benzanthracene.
7. The method for preparing the dianthracene D-delta-A type deep blue organic fluorescent material according to claim 2, which is characterized in that: in the Suzuki coupling reaction, a catalyst, a solvent and an activating agent are also added; wherein the ratio of the substances 7a, 9- (4-electroabsorption substituted phenyl) -10 borate anthracene, the catalyst, the solvent and the activator is (0.25-1) mmol: (0.21-0.84) mmol: (0.03-0.12) mmol: (25-100) mL: (8.4-33.6) mmol; the catalyst adopts tetra (triphenylphosphine) palladium; the solvent adopts a mixed solvent of toluene and homogeneous solvent ethanol; k is used as activator 2 CO 3 A solution;
the Suzuki coupling reaction is carried out for 12-24 hours at the temperature of 100-110 ℃ under the atmosphere of nitrogen gas.
8. The use of the dianthracene D-delta-a deep blue organic fluorescent material according to claim 1 in an organic electroluminescent diode device.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001855A (en) * | 2015-06-11 | 2015-10-28 | 中节能万润股份有限公司 | Blue-fluorescence material and application thereof |
| CN109265310A (en) * | 2018-11-21 | 2019-01-25 | 陕西师范大学 | A kind of organic blue fluorescent material and its preparation method and application |
| CN109678759A (en) * | 2018-12-28 | 2019-04-26 | 陕西师范大学 | Organic blue fluorescent material of a kind of D-A type based on dianthracene and its preparation method and application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105001855A (en) * | 2015-06-11 | 2015-10-28 | 中节能万润股份有限公司 | Blue-fluorescence material and application thereof |
| CN109265310A (en) * | 2018-11-21 | 2019-01-25 | 陕西师范大学 | A kind of organic blue fluorescent material and its preparation method and application |
| CN109678759A (en) * | 2018-12-28 | 2019-04-26 | 陕西师范大学 | Organic blue fluorescent material of a kind of D-A type based on dianthracene and its preparation method and application |
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