CN109503427A - A kind of organic blue fluorescent material of D-A type and its preparation method and application - Google Patents

A kind of organic blue fluorescent material of D-A type and its preparation method and application Download PDF

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CN109503427A
CN109503427A CN201811619632.0A CN201811619632A CN109503427A CN 109503427 A CN109503427 A CN 109503427A CN 201811619632 A CN201811619632 A CN 201811619632A CN 109503427 A CN109503427 A CN 109503427A
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benzene
anthracene
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CN109503427B (en
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胡鉴勇
张佳丽
赵振
段雪伟
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Shaanxi Normal University
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Abstract

The present invention relates to organic blue fluorescent materials of a kind of D-A type and its preparation method and application, the MOLECULE DESIGN strategy of the material is the pi-conjugated bridge chain centered on benzene, being separately connected two anthracene luminescence units on position therebetween, (one has the group of donor properties, one has the group of electrophilic characteristic), come pi-conjugated form and the Intramolecular electron transfer path of controlled material molecule, it realizes the dark blue transmitting of material molecule, and realizes the injection balance of the carrier in OLED device application.On the other hand, the group of the group or electrophilic characteristic with donor properties is introduced on the pi-conjugated bridge chain of center benzene, to further suppress the effect of the π-π stacking between material molecule, realize the high luminous quantum efficiency of material molecule, a kind of organic blue fluorescent material of D-A type is prepared, the thermal stability and high luminous quantum efficiency which has had.

Description

A kind of organic blue fluorescent material of D-A type and its preparation method and application
[technical field]
The present invention relates to organic electroluminescent LED fields, and in particular to a kind of organic blue fluorescent material of D-A type and Preparation method and application.
[background technique]
Compared with traditional liquid crystal display (LCD), organic electroluminescent LED (Organic Light-Emitting Diodes, OLED), because its have the characteristics that all solid state, self-luminous, wide viewing angle, low voltage drive, can be flexible, it is considered to be it is new A generation is shown and the most competitive technology of all solid state lighting area.By effort in 30 years, OLED brightness, efficiency, Service life etc. all achieves huge progress, and Commercial Prospect has made first appearance.Nevertheless, still there is blue lights by OLED Material and the problems such as device lifetime is short, low efficiency, makees further explore up for scientific research person.
In order to realize full-color EL display, three primary colours (feux rouges, green light, blue light) are essential.It is currently used in OLED In feux rouges and green light material relative maturity, be able to satisfy commercialized requirement, but blue material substantially, especially efficiently Stable navy blue luminescent material is relatively fewer, this largely affects the industrialization process of OLED.For excellent For blue light material, the excitation purity that has not only needed, it is also necessary to good thermal stability, high luminous efficiency and the easily property such as distillation Can, therefore good blue light material, especially dark blue luminescent material are difficult to obtain.Up to the present, although the derivative of many anthracenes Object blue light material is developed, and is successfully applied in OLED device as main body or guest emitting material, but due to these materials Material mostly has the characteristics that synthesis is difficult, is not easily purified, easily crystallization, stability is poor, causes OLED device low efficiency, service life short.Cause This, the organic blue luminescent material for further developing efficient stable has more real meaning to the commercialization process for pushing OLED Justice.
[summary of the invention]
It is an object of the invention to overcome the above-mentioned prior art, a kind of organic blue fluorescent material of D-A type is provided And its preparation method and application；Prepared material thermal stability is good and luminous quantum efficiency is high, applies undoped dark blue In OLED device, performance is excellent, external quantum efficiency (EQE) is high.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
A kind of organic blue fluorescent material of D-A type, structural formula are as follows:
Wherein: R1The group of confession under directions characteristic electron, R2Refer to the group of electrophilic characteristic, R3、R4Refer to neutral group, supplied for electronic The group of characteristic or the group of electrophilic characteristic.
A further improvement of the present invention is that:
Preferably, wherein R1For CH3、OCH3、C2H5、OC2H5Or C (CH3)3；R2For F, CF3, CN or CHO；R3、R4For H, CH3、OCH3、C2H5、OC2H5、C(CH3)3、F、CF3, CN or CHO.
A kind of preparation method of the organic blue fluorescent material of D-A type, using substance B and the bromo- 10- of 9- (4- electrophilic substitution) Benzene anthracene carries out Suzuki coupling reaction and is made, and the substance B is 3- [10- (substitution of 4- supplied for electronic) benzene anthracene] -4,5,6- trisubstituted benzenes Borate；Wherein the electrophilic in the bromo- 10- of 9- (4- electrophilic substitution) benzene anthracene is substituted by F, CF3, any one of CN or CHO； Supplied for electronic is substituted by CH in 3- [10- (substitution of 4- supplied for electronic) benzene anthracene] -4,5,6- trisubstituted benzene borate3、OCH3、C2H5、OC2H5 Or C (CH3)3Any one of, the substituent group in 4,5,6- trisubstituted benzene borates is the base of neutral group, donor properties Any one of group or any one of the group of electrophilic characteristic, neutral group are H；The group of donor properties includes CH3、 OCH3、C2H5、OC2H5With C (CH3)3；The group of electrophilic characteristic includes F, CF3, CN and CHO.
Preferably, substance B is to be made by substance A by acid esterification, and substance A is 3- [10- (substitution of 4- supplied for electronic) benzene Anthracene] the substitution chlorobenzene of -4,5,6- three；Specific steps include: by 0.5~2mmol of substance A, connection boric acid pinacol ester 1.5~ 6mmol, acid chloride 0.05~0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 ' -0.1~0.4mmol of dimethoxy-biphenyl, potassium acetate 1.5~6mmol and Isosorbide-5-Nitrae -25~90mL of dioxane mixing, after being vacuumized to system under the protection of nitrogen, at 95~105 DEG C Lower reaction 12~18 hours extracts after reaction, revolving, and column chromatography is recrystallized to give substance B.
Preferably, substance A is taken by 9- (4- power supply substituted-phenyl) -10 borate anthracenes and the chloro- 3- of 1- iodo- 4,5,6- tri- Carry out what Suzuki coupling reaction obtained for benzene, specific steps include: that 9- (4- power supply substituted-phenyl) -10 borate anthracenes, 1- is chloro- The iodo- 4,5,6- trisubstituted benzene of 3-, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3Solution presses (1~3) mmol:(1~3) Mmol:(0.1~0.3) mmol:(40~120) mL:(10~30) mL:(40~120) mmol mixing, under nitrogen protection, 100 ~110 DEG C reaction 12~24 hours after obtain intermediate product, intermediate product is extracted, rotate, column chromatography, be recrystallized to give substance A。
Preferably, 9- (4- power supply substituted-phenyl) -10 borate anthracenes are by the bromo- 10- of 9- (4- power supply replaces) benzene anthracene borate Change and is made, specifically includes the following steps: by the bromo- 10- of the 9- of 4.22~12.66mmol (4- power supply replaces) benzene anthracene, 6.32~ The isopropyl oxygen borate of 18.96mmol, the n-BuLi (being added at -78 DEG C) of 7.2~21.6mmol, the THF of 50~150mL After mixing, under the protection of nitrogen, reacts 8~12 hours, after reaction, extract, revolving at room temperature, column chromatography, recrystallization Obtain 9- (4- power supply substituted-phenyl) -10 borate anthracenes.
Preferably, the bromo- 10- of 9- (4- power supply replaces) benzene anthracene is to be obtained by 9- (4- power supply replaces) benzene anthracene by bromination , specific steps include: by 9- (4- power supply replaces) benzene anthracene, N- bromo-succinimide and n,N-Dimethylformamide by (2.5 ~10) mmol:(3~12) mmol:(40~150) mL mixing, under nitrogen gas ambient conditions, 85~90 DEG C of reactions 1~2 are small When, methanol washs and filters to obtain the bromo- 10- of 9- (4- power supply replaces)；
9- (4- power supply replaces), benzene anthracene was that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: 9- bromine anthracene, 4- power supply are replaced into phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5 ~30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in inert gas atmosphere Under the conditions of enclosing, 100~110 DEG C after back flow reaction 12~24 hours by extraction, revolving, column chromatography, being recrystallized to give 9-, (4- is supplied Electricity replaces) benzene anthracene.
Preferably, the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene is to be obtained by 9- (4- inhales electricity and replaces) benzene anthracene by bromination , specific steps include: by 9- (4- inhales electricity and replaces) benzene anthracene, N- bromo-succinimide and n,N-Dimethylformamide by (2.5 ~10) mmol:(3~12) mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C of reactions 1~2 are small When, methanol washing reaction product, suction filtration obtains the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene；
9- (4- inhales electricity and replaces) benzene anthracene is that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: 9- bromine anthracene, 4- are inhaled into electric substituent group phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol: (7.5~30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in nitrogen atmosphere Under enclosing, 100~110 DEG C back flow reaction 12~24 hours, after reaction, extract, revolving, column chromatography, be recrystallized to give 9- (4- Electricity is inhaled to replace) benzene anthracene.
Preferably, in Suzuki coupling reaction, catalyst, solvent and activator have been additionally added；Wherein, the bromo- 10- of substance B, 9- The ratio of (4- electrophilic substitution) between benzene anthracene, catalyst, toluene, ethyl alcohol and activator be (0.25~1) mmol:(0.21~ 0.84) mmol:(0.03~0.12) mmol:(15~60) mL:(5~20) mmol:(8.4~33.6) mmol；Catalyst uses Tetrakis triphenylphosphine palladium；Activator uses K2CO3Solution；Suzuki coupling reaction, be under nitrogen gas ambient conditions, 100~ At 110 DEG C, react 12~24 hours, after reaction, methanol hot wash filters, re crystallization from toluene, and distillation obtains final product.
A kind of application of the organic blue fluorescent material of above-mentioned D-A type in organic electroluminescent diode apparatus.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of organic blue fluorescent material of D-A type, which is dianthracene analog derivative, can be realized depth Blue emission.The present invention uses pi-conjugated bridge chain centered on benzene, is separately connected two anthracene luminescence units (one on position therebetween Group with donor properties, one has the group of electrophilic characteristic), realize to the conjugation form of organic material molecule and The regulation in Intramolecular electron transfer path (ICT) realizes that the dark blue of material molecule shines, and to realize in OLED device application The balance of carrier injection.Meanwhile by introducing the group with donor properties or electrophilic on the pi-conjugated bridge chain of center benzene The group of characteristic effectively to inhibit the intermolecular pi-pi accumulation of organic material, realizes the high luminous quantum efficiency of material.By adopting With bridge chain pi-conjugated centered on benzene, being separately connected two anthracene luminescence units on position therebetween, (one has the base of donor properties Group, one has the group of electrophilic characteristic), regulate and control conjugation form, the Intramolecular electron transfer path of organic molecule, Yi Jishi The balance of carrier injection in the dark blue transmitting and OLED device application of existing material molecule；Meanwhile drawing on central pi-conjugated bridge chain Enter space steric hindrance group to eliminate the intermolecular π-π of organic material and stack interaction, realizes high luminous quantum efficiency；Non- It adulterates in OLED device, realizes dark blue light emitting, excitation purity is high, and performance is excellent, can reduce cost of manufacture, simplifies production technology. In short, the invention has the characteristics that 1) connecting two anthracenes using two meta position using pi-conjugated bridge chain centered on benzene and shining Unit realizes the conjugation form to organic molecule, excitation state electric charge transfer, stacked state and the charge in OLED device application The regulation of injection balance；2) group of the group or electrophilic characteristic with donor properties is introduced on central pi-conjugated bridge chain, It interacts to further suppress the π-π between organic molecule, improves the luminous quantum efficiency of material molecule, realize dark blue transmitting.
The invention also discloses a kind of preparation method of the organic blue fluorescent material of D-A type, this method is with benzene for pi-conjugated bridge Chain is separately connected two (one has the group of donor properties, and one has the group of electrophilic characteristic) therebetween on position Anthracene luminescence unit is further implemented in realize to the regulation of the conjugation form, excitation state charge transfer path of organic molecule The injection balance of carrier in OLED device application, while the group with donor properties is introduced on central pi-conjugated bridge chain Or the group of electrophilic characteristic improves the luminous quantity of material molecule to further suppress the interaction of the π-π between organic molecule Sub- efficiency realizes dark blue light emitting, be successfully prepared the thermal stability provided, high fluorescence quantum efficiency it is organic dark blue Fluorescent material；It is entire that synthesis step is simple, yield is high, material is easily purified.
The invention also discloses a kind of organic blue fluorescent material of D-A type answering in organic electroluminescent diode apparatus With.The organic blue fluorescent material prepared, under ultraviolet light, strong navy blue fluorescence hair is all presented in solution or film It penetrates.The luminescent material based on organic blue fluorescent material successfully prepares the undoped dark blue OLED device of high-performance；It should Class material is applied in undoped OLED, and EQE (~3.66%) is much higher than theoretical calculation EQE value (~0.6%), [EQEIt is theoretical= ηeh·ηPL·ηexciton·ηout=1 × 0.08 × 0.25 × 0.3=0.6%], wherein ηehIt is the recombination rate of electrons and holes； ηPLFor the fluorescence quantum yield η of net filmexcitonThe ratio of exciton；ηoutFor light transmittance.
[Detailed description of the invention]
Fig. 1 is the nuclear magnetic spectrum of organic blue fluorescent material made from the embodiment of the present invention 1.
Fig. 2 is the mass-spectrogram of organic blue fluorescent material made from the embodiment of the present invention 1.
Fig. 3 is the thermogravimetric map of anthracene derivative a made from 1-3 of the embodiment of the present invention.
Fig. 4 is absorption spectrum of organic blue fluorescent material in different solutions made from the embodiment of the present invention 1.
Fig. 5 is emission spectrum of organic blue fluorescent material in different solutions made from the embodiment of the present invention 1.
Fig. 6 is Absorption and emission spectra of organic blue fluorescent material on film made from the embodiment of the present invention 1.
Fig. 7 is electroluminescent (EL) map of device 1 produced by the present invention.
Fig. 8 is Current density-voltage-brightness (Cd-V-L) graphs of device 1 produced by the present invention.
Fig. 9 is that current efficiency-current density-power efficiency (CE-Cd-PE) map of device 1 produced by the present invention is bent Line.
Figure 10 is the graphs of current density-external quantum efficiency (Cd-EQE) of device 1 produced by the present invention.
[specific embodiment]
The invention will be described in further detail with specific steps with reference to the accompanying drawing:
The invention discloses organic blue fluorescent materials of a kind of D-A type and its preparation method and application；The invention by pair The sophisticated design of material molecule, wherein the pi-conjugated bridge chain centered on benzene is separately connected two anthracene luminescence units therebetween on position (one have donor properties group, one have electrophilic characteristic group), come regulate and control organic molecule conjugation form, Charge in dark blue transmitting and OLED device application is realized in excitation state charge transfer path and the effect of intermolecular π-π stacking Injection balance, meanwhile, at center, the pi-conjugated bridge chain of benzene is imported, and there is the group of donor properties or electrophilic characteristic further to press down π-π stacking effect between organic molecule processed, realizes the High Efficiency Luminescence of material molecule.The organic blue fluorescent material tool prepared The thermal stability and high luminous quantum efficiency having had.Its chemical structural formula is as follows.
Wherein R1For the group of donor properties, R2For the group of electrophilic characteristic, R3、R4For neutral group or supplied for electronic The group of characteristic or the group of electrophilic characteristic, the group of donor properties are preferred are as follows: CH3、OCH3、C2H5、OC2H5Or C (CH3)3；The group of electrophilic characteristic is preferably F, CF3, CN or CHO；Neutral group is preferably H；The organic blue synthesized is glimmering Shown in the chemical structural formula of luminescent material is exemplified below:
It is followed successively by compound a, compound b, compound c, compound d, compound e, compound f, compound g, compound H, compound i, compound j, compound m, compound n, compound o, compound p；Wherein compound is R1、R2、R3、R4Middle group Any one closed, above-mentioned chemical formula only enumerates a part, R1、R2、R3And R4See Table 1 for details for optional group.
1 R of table1、R2、R3And R4Optional group
R1 CH3、OCH3、C2H5、OC2H5Or C (CH3)3
R2 F、CF3, CN or CHO
R3、R4 H、CH3、OCH3、C2H5、OC2H5、C(CH3)3、F、CF3, CN or CHO
Shown in the specific synthetic route such as following formula (1) of organic blue fluorescent material of the invention:
2a in above formula is referred to3a is referred to4a is referred toIt is corresponding 2b is referred to3b is referred to4b is referred to
By taking the synthesis of compound a as an example, shown in specific synthetic route such as following formula (2):
By taking the synthesis of compound b as an example, shown in specific synthetic route such as following formula (3):
The detailed process of synthesis process the following steps are included:
Step 1, the group of donor properties is synthesized
1. by 5~20mmol of 9- bromine anthracene, 4- power supply substitution phenyl boric acid (2a) 7.5~30mmol, solution of potassium carbonate 15~ 60mL, 50~200mL of toluene, 15~60mL of ethyl alcohol are added to reaction flask, and wherein solution of potassium carbonate is by 50~200mmol carbonic acid Proportion in 15~60mL water is added in potassium solid；It is eventually adding 0.25~1mmol tetrakis triphenylphosphine palladium.Then system is taken out Vacuum under nitrogen protection, flows back 12~24 hours at 100~110 DEG C.After reaction, it extracts, revolving, column chromatography, recrystallization Obtain 9- (4- power supply replaces) benzene anthracene (3a)；Wherein, power supply is substituted by any one of group of donor properties, including CH3、 OCH3、C2H5、OC2H5With C (CH3)3。
The bromination of 9- 2. (4- power supply replaces) benzene anthracene: by 9- (4- power supply replaces) (3a) benzene anthracene 2.50~10mmol, N, N- Dimethylformamide (DMF) 40~150mL, N- bromo-succinimide (NBS) 3~12mmol is added to reaction flask, then right System vacuumizes, and under nitrogen protection, 85~90 DEG C are reacted 1~2 hour, and methanol washing reaction product, suction filtration obtains the bromo- 10- of 9- (4- power supply replaces) benzene anthracene (4a).
Step 2, the group of electrophilic characteristic is synthesized
1. by 5~20mmol of 9- bromine anthracene, 4- suction electricity substituent group phenyl boric acid (2b) 7.5~30mmol, solution of potassium carbonate 15~ 60mL, 50~200mL of toluene, 15~60mL of ethyl alcohol are added to reaction flask, and wherein solution of potassium carbonate is by 50~200mmol carbonic acid Proportion in 15~60mL water is added in potassium solid；It is eventually adding 0.25~1mmol tetrakis triphenylphosphine palladium.Then system is taken out Vacuum under nitrogen protection, flows back 12~24 hours at 100~110 DEG C.After reaction, it extracts, revolving, column chromatography, recrystallization Obtain 9- (4- inhales electricity and replaces) benzene anthracene (3b)；Wherein, electric any one of the group for being substituted by electrophilic characteristic of suction, including F, CF3、CN、CHO。
The bromination of 9- 2. (4- inhales electricity and replaces) benzene anthracene: by 9- (4- inhales electricity and replaces) benzene anthracene (3b) 2.50~10mmol, N, N- Dimethylformamide (DMF) 40~150mL, N- bromo-succinimide (NBS) 3~12mmol is added to reaction flask, then right System vacuumizes, and under nitrogen protection, 85~90 DEG C are reacted 1~2 hour, and methanol washing reaction product, suction filtration obtains the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene (4b).
Step 3, the synthesis process of final product
The acid esterification of the bromo- 10- of 9- 1. (4- power supply replaces) benzene anthracene: by the bromo- 10- of 9- made from step 1, (4- power supply is taken Generation) benzene anthracene (4a) 4.22~12.66mmol, isopropyl oxygen 6.32~18.96mmol of borate, 7.2~21.6mmol of n-BuLi (being added at -78 DEG C), 50~150mL of THF is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, room temperature Lower stirring 8~12 hours.After reaction, it extracts, revolving, column chromatography, is recrystallized to give product 9- (4- power supply substituted-phenyl)- 10 borate anthracenes (5a).
The Suzuki coupling reaction of 9- 2. (4- power supply substituted-phenyl) -10 borate anthracenes: by 9- (4- power supply substituted-phenyl) - Iodo- 4,5,6- 1~3mmol of trisubstituted benzene of the 10 chloro- 3- of borate anthracene (5a) 1~3mmol, 1-, tetrakis triphenylphosphine palladium 0.1~ 0.3mmol, 40~120mL of toluene, ethyl alcohol 10~30mL and K2CO340~120mmol of solution (is dissolved in 10~30mL distilled water It is made) it is added to reaction flask, then system is vacuumized, under the protection of nitrogen, is reacted 12~24 hours at 100~110 DEG C, After reaction, it extracts, revolving, column chromatography, is recrystallized to give product A, 3- [10- (4- power supply replaces) benzene anthracene] -4,5,6- tri- Replace chlorobenzene；Substituent group in the iodo- 4,5,6- trisubstituted benzene of the chloro- 3- of 1- among the above is R3、R4, R3And R4For supplied for electronic Any one of group of characteristic or any one of the group of electrophilic characteristic or neutral group, neutral group are H；Supplied for electronic The group of characteristic includes CH3、OCH3、C2H5、OC2H5With C (CH3)3；The group of electrophilic characteristic includes F, CF3, CN and CHO.
3. the acid esterification of A reacts: by 0.5~2mmol of A, 1.5~6mmol of connection boric acid pinacol ester, acid chloride 0.05 ~0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls (S-Phos) 0.1~0.4mmol, potassium acetate (KOAc) 1.5 ~6mmol and Isosorbide-5-Nitrae-dioxane (Isosorbide-5-Nitrae-dioxane) 25~90mL are mixed to join reaction flask, then vacuumize to system, It under the protection of nitrogen, reacts 12~18 hours, after reaction, extracts, revolving at 95~105 DEG C, column chromatography recrystallizes To substance B；
Product B is 3- [10- (4- power supply replaces) benzene anthracene] -4,5,6- tri-substituted phenyl borates, wherein 4,5,6- tri- take It is respectively 5- methyl -4,6- dihydro phenyl, fluoro- 4, the 6- dihydro phenyl of 5-, 5- methoxyl group -4,6- dihydro phenyl, 5- second for phenyl Base -4,6- dihydro phenyl, 5- ethyoxyl -4,6- dihydro phenyl, 5- tert-butyl -4,6- dihydro phenyl, 5- cyano -4,6- dihydrobenzene Base, 5- trifluoromethyl -4,6- dihydro phenyl, 5- hydrogen -4,6- Dimethoxyphenyl, 5- hydrogen -4,6- 3,5-dimethylphenyl, hydrogen -4 5-, 6- dialdehyde-based phenyl, 5- hydrogen -4,6- dicyano phenyl, tri- hydrogen phenyl of 4,5,6-, 4,5,6- trimethoxyphenyl, 4,5,6- front three Base phenyl or 4,5,6- trifluorophenyl.
Above-mentioned 4,5,6- tri-substituted phenyls are only enumerated a part, wherein three substitutions can be electron donating group, suction Any one in electron substituent group or neutral group.
4. the synthesis of final product: by 0.25~1mmol of substance B, (4- inhales electricity and takes the bromo- 10- of step 2 products therefrom 4b, that is, 9- Generation) benzene 0.21~0.84mmol of anthracene, catalyst four (triphenyl) phosphine 0.03~0.12mmol of palladium, 15~60mL of toluene, ethyl alcohol 5~ 20mL, K2CO38.4~33.6mmol (with 5~20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, 100~110 DEG C of reflux 12~for 24 hours.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product, are Organic blue fluorescent material.
The solution of potassium carbonate of addition is so that it is converted into active reaction intermediate in order to activate borate ion.Add second Alcohol is the hydrophily in order to increase solvent, carries out reaction under homogeneous phase condition.
Intermediate product A in following example1~A16It indicates because of R3、R4The intermediate product that group is different and synthesizes is different, B1 ~B16Similarly.
Embodiment 1
Step 1, the group of donor properties is synthesized: 1. by 9- bromine anthracene 5mmol, 4- methoxyphenylboronic acid 7.5mmol, carbonic acid Potassium solution 50mmol (uses 15mL distilled water wiring solution-forming), and toluene 50mL, ethyl alcohol 15mL is added to reaction flask, is eventually adding 0.25mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, is flowed back 12 hours at 100 DEG C.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=4:1), is recrystallized to give 9- (4- methoxyl group) benzene anthracene. Yield 86%.2. by 9- (4- methoxyl group) benzene anthracene 2.50mmol, n,N-Dimethylformamide (DMF) 40mL, N- bromo succinyl Imines (NBS) 3mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 85 DEG C are reacted 1 hour.Methanol is washed It washs, suction filtration obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 89%.
Step 2, synthesize electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- Methoxyl group) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: 1. carries out on the basis of step 1 in next step, by 9- bromo- 10- (4- methoxy Base) benzene anthracene 4.22mmol, isopropyl oxygen borate 6.32mmol, n-BuLi 7.2mmol (being added at -78 DEG C), THF 50mL It is added to reaction flask, then system is vacuumized, under the protection of nitrogen, is stirred 8 hours at room temperature.After reaction, it extracts, rotation It steams, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give -10 borate anthracene of product 9- (4- methoxyl group). Yield 80%.2. by iodo- 4,5,6- tri- hydrogen substituted benzene 1mmol of -10 chloro- 3- of borate anthracene 1mmol, 1- of 9- (4- methoxyl group), four (triphenylphosphine) palladium 0.1mmol, toluene 40mL, ethyl alcohol 10mL and K2CO340mmol (with 10mL distilled water wiring solution-forming) is added to Then reaction flask vacuumizes system, the protection of nitrogen, reacts 12 hours, after reaction, extracts, revolving, column at 100 DEG C It chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A1.Yield 68%.3. by A10.5mmol joins boron Sour pinacol ester 1.5mmol, acid chloride 0.05mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.1mmol, acetic acid Potassium 1.5mmol, Isosorbide-5-Nitrae-dioxane 25mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, anti-at 90 DEG C It answers 12 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give Product B1.Yield 70%.4. obtaining final product a by Suzuki (Suzuki) coupling reaction: by B10.25mmol is produced obtained by step 2 The bromo- 10- of object, that is, 9- (4- cyano) benzene anthracene 0.21mmol, catalyst four (triphenyl) phosphine palladium 0.03mmol, toluene 15mL, ethyl alcohol 5mL, K2CO38.4mmol (uses 5mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, flows back at 100 DEG C 12h.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 78%.Nuclear magnetic resonance point Analysis: NMR (400MHz)1δ=8.04-7.92 (m, 2H) H NMR (400MHz), 7.86 (d, J=7.7,1H), 7.75 (d, J= 8.4,1H), 7.61 (s, 1H), 7.53 (d, J=8.5,1H), 7.48-7.30 (m, 5H), 7.25 (s, 4H), 3.95 (s, 2H), 1.56 (s, 7H) nuclear magnetic spectrums are illustrated in fig. 1 shown below.Mass spectrum (m/s), molecular formula C48H31NO, theoretical value 637.24 are practical Value is 637, and mass-spectrogram is illustrated in fig. 2 shown below.
Embodiment 2
The group of step 1 synthesis donor properties: 1. by 9- bromine anthracene 10mmol, 4- methoxyphenylboronic acid 15mmol, carbonic acid Potassium solution 100mmol (uses 30mL distilled water wiring solution-forming), and toluene 136mL, ethyl alcohol 30mL is added to reaction flask, is eventually adding 0.5mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, 105 lower reflux 18 hours.After reaction, Extraction, revolving, column chromatograph (eluant, eluent: n-hexane/methylene chloride=4:1), are recrystallized to give 9- (4- methoxyl group) benzene anthracene.Yield 90%.2. by 9- (4- methoxyl group) benzene anthracene 5mmol, n,N-Dimethylformamide (DMF) 75mL, N- bromo-succinimide (NBS) 6mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 88 DEG C are reacted 1.5 hours.Methanol washing, Suction filtration obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 89%.
Step 2 synthesis electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- Methoxyl group) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: 1. carries out on the basis of step 1 in next step, by 9- bromo- 10- (4- methoxy Base) benzene anthracene 8.44mmol, isopropyl oxygen borate 12.64mmol, n-BuLi 14.4mmol (being added at -78 DEG C), THF100mL is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, stirs 10 hours at room temperature.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product 9- (4- methoxyl group)- 10 borate anthracenes, yield 70%.2. iodo- 4,5,6- tri- hydrogen of -10 chloro- 3- of borate anthracene 2mmol, 1- of 9- (4- methoxyl group) is replaced Benzene 2mmol, tetrakis triphenylphosphine palladium 0.2mmol, toluene 80mL, ethyl alcohol 20mL and K2CO380mmol (is made into 20mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 12 hours, after reaction, extraction are reacted at 100 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A1.Yield 69%.3. will A11mmol, connection pinacol borate 3mmol, acid chloride 0.1mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.2mmol, potassium acetate 3mmol, Isosorbide-5-Nitrae-dioxane 45mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protecting, reacts at 95 DEG C 16 hours, after reaction, extract, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), It is recrystallized to give product B1.Yield 65%.4. obtaining final product a by Suzuki (Suzuki) coupling reaction: by B10.5mmol, step The bromo- 10- of rapid 2 products therefroms, that is, 9- (4- cyano) benzene anthracene 0.42mmol, catalyst four (triphenyl) phosphine palladium 0.06mmol, toluene 30mL, ethyl alcohol 10mL, K2CO316.8mmol (uses 10mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, In 105 DEG C of reflux 18h.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 75%. Molecular formula is C48H31NO, theoretical value 637.24, actual value 637.
Embodiment 3
The group of step 1 synthesis donor properties: 1. by 9- bromine anthracene 20mmol, 4- methoxyphenylboronic acid 30mmol, carbonic acid Potassium solution 200mmol (uses 60mL distilled water wiring solution-forming), and toluene 200mL, ethyl alcohol 60mL is added to reaction flask, is eventually adding 1mmol tetrakis triphenylphosphine palladium.Then system is vacuumized, under nitrogen protection, is flowed back 24 hours at 110 DEG C.After reaction, Extraction, revolving, column chromatograph (eluant, eluent: n-hexane/methylene chloride=4:1), are recrystallized to give 9- (4- methoxyl group) benzene anthracene.Yield 89%.2. by 9- (4- methoxyl group) benzene anthracene 10mmol, n,N-Dimethylformamide (DMF) 150mL, N- bromo-succinimide (NBS) 12mmol is added to reaction flask, then vacuumizes to system, and under nitrogen protection, 90 DEG C are reacted 2 hours.Methanol washing, takes out Filter obtains the bromo- 10- of product 9- (4- methoxyl group) benzene anthracene, yield 90%.
Step 2 synthesis electrophilic characteristic group: with step 1 [only need to by 1. 2. in 4- methoxyphenylboronic acid, 9- (4- Methoxyl group) benzene anthracene replaces with 4- cyanophenylboronic acid, 9- (4- cyano) benzene anthracene].
Step 3, it the synthesis process of final product: 1. carries out on the basis of step 1 in next step, by 9- bromo- 10- (4- methoxy Base) benzene anthracene 12.66mmol, isopropyl oxygen borate 18.96mmol, n-BuLi 21.60mmol (being added at -78 DEG C), THF150mL is added to reaction flask, then vacuumizes to system, under the protection of nitrogen, stirs 12 hours at room temperature.Reaction terminates Afterwards, it extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give product 9- (4- methoxyl group)- 10 borate anthracenes, yield 68%.2. iodo- 4,5,6- tri- hydrogen of -10 chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methoxyl group) is replaced Benzene 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is matched with 30mL distilled water At solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, reacts 24 hours at 110 DEG C, after reaction, Extraction, revolving, column chromatograph (eluant, eluent: n-hexane/methylene chloride=1:1), are recrystallized to give product A1.Yield 66%.3. will A12mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B1, yield 68%.4. obtaining final product a by Suzuki (Suzuki) coupling reaction: by B11mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 78%. Molecular formula is C48H31NO, theoretical value 637.24, actual value 637.
Embodiment 4
In steps 1 and 2 and step 3 1. with embodiment 3.
2. by -10 iodo- 5- methyl -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methoxyl group) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A2.Yield 66%.3. will A22mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B2, yield 68%.4. obtaining final product b by Suzuki (Suzuki) coupling reaction: by B21mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 68%. Molecular formula is C49H33NO, theoretical value 651.26, actual value 651.
Embodiment 5
In steps 1 and 2 and step 3 1. with embodiment 3.
2. by -10 fluoro- 4, the 6- dihydro substituted benzene 3mmol of the iodo- 5- of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methoxyl group), Tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (uses 30mL distilled water wiring solution-forming) It is added to reaction flask, then system is vacuumized, the protection of nitrogen is reacted at 110 DEG C 24 hours, after reaction, extracted, rotation It steams, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A3.Yield 66%.3. by A32mmol, Connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.4mmol, acetic acid Potassium 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, anti-at 105 DEG C It answers 18 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give Product B3, yield 68%.4. obtaining final product c by Suzuki (Suzuki) coupling reaction: by B31mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, returns at 110 DEG C Stream is for 24 hours.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 69%.Molecular formula is C48H30FNO, theoretical value 655.23, actual value 655.
Embodiment 6
In steps 1 and 2 and step 3 1. with embodiment 3.It (only need to be by 1. middle 4- methoxyphenylboronic acid, the 4- of steps 1 and 2 Cyanophenylboronic acid replaces with 4- methylphenylboronic acid, 4- fluorobenzoic boric acid respectively).
2. by -10 iodo- 5- methoxyl group -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methyl) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A4.Yield 66%.3. will A42mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B4, yield 68%.4. obtaining final product d by Suzuki (Suzuki) coupling reaction: by B41mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- fluorine) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 70%. Molecular formula is C48H33FO, theoretical value 644.25, actual value 644.
Embodiment 7
In steps 1 and 2 and step 3 1. with embodiment 6.(only the 1. middle 4- fluorobenzoic boric acid of step 2 need to be replaced with 4- Trifluoro phenyl boric acid).
2. by -10 iodo- 5- ethyl -4, the 6- dihydro substituted benzene 3mmol of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methyl), Tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (uses 30mL distilled water wiring solution-forming) It is added to reaction flask, then system is vacuumized, the protection of nitrogen is reacted at 110 DEG C 24 hours, after reaction, extracted, rotation It steams, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A5.Yield 66%.3. by A52mmol, Connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyl 0.4mmol, acetic acid Potassium 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the protection of nitrogen, anti-at 105 DEG C It answers 18 hours, after reaction, extracts, revolving, column chromatographs (eluant, eluent: n-hexane/methylene chloride=2:1), is recrystallized to give Product B5, yield 68%.4. obtaining final product e by Suzuki (Suzuki) coupling reaction: by B51mmol, step 2 products therefrom That is the bromo- 10- of 9- (4- trifluoro) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, returns at 110 DEG C Stream is for 24 hours.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 70%.Molecular formula is C50H35F3, theoretical value 692.27, actual value 692.
Embodiment 8
In steps 1 and 2 and step 3 1. with embodiment 6.(the 1. middle 4- methylphenylboronic acid of step 1 need to only be replaced respectively It is changed to 4- ethyl phenyl boric acid).
2. by -10 iodo- 5- ethyoxyl -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- ethyl) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A6.Yield 68%.3. will A62mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B6, yield 68%.4. obtaining final product f by Suzuki (Suzuki) coupling reaction: by B61mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- fluorine) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 66%. Molecular formula is C50H37FO, theoretical value 672.28, actual value 672.
Embodiment 9
In steps 1 and 2 and step 3 1. with embodiment 3.It (only need to be by 1. middle 4- methoxyphenylboronic acid, the 4- of steps 1 and 2 Cyanophenylboronic acid replaces with 4- ethoxybenzene boric acid, 4- aldehyde radical phenyl boric acid respectively).
2. by -10 iodo- 5- tert-butyl -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- ethyoxyl) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A7.Yield 66%.3. will A72mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B7, yield 68%.4. obtaining final product g by Suzuki (Suzuki) coupling reaction: by B71mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- aldehyde radical) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 70%. Molecular formula is C49H33O2, theoretical value 653.25, actual value 653.
Embodiment 10
In steps 1 and 2 and step 3 1. with embodiment 9.It (only need to be by the 1. middle 4- ethoxybenzene boric acid replacement of step 1 For 4- tert-butylbenzeneboronic acid).
2. by -10 iodo- 5- cyano -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- tert-butyl) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A8.Yield 66%.3. will A82mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B8, yield 68%.4. obtaining final product h by Suzuki (Suzuki) coupling reaction: by B81mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- aldehyde radical) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 68%. Molecular formula is C48H28NO, theoretical value 634.22, actual value 634.
Embodiment 11
In steps 1 and 2 and step 3 1. with embodiment 3.
2. by -10 iodo- 5- trifluoromethyl -4, the 6- dihydro substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methoxyl group) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A9.Yield 69%.3. will A92mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B9, yield 68%.4. obtaining final product i by Suzuki (Suzuki) coupling reaction: by B91mmol, The step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, under the protection of nitrogen, It flows back for 24 hours at 110 DEG C.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.Yield 69%. Molecular formula is C49H30F3NO, theoretical value 705.23, actual value 705.
Embodiment 12
In steps 1 and 2 and step 3 1. with embodiment 3.
2. by -10 iodo- 4, the 6- dimethoxy -5- hydrogen substituted benzene of the chloro- 3- of borate anthracene 3mmol, 1- of 9- (4- methoxyl group) 3mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 120mL, ethyl alcohol 30mL and K2CO3120mmol (is made into 30mL distilled water Solution) it is added to reaction flask, then system is vacuumized, the protection of nitrogen, 24 hours, after reaction, extraction are reacted at 110 DEG C It takes, rotates, column chromatographs (eluant, eluent: n-hexane/methylene chloride=1:1), is recrystallized to give product A10.Yield 69%.3. will A102mmol, connection pinacol borate 6mmol, acid chloride 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 '-dimethoxy-biphenyls 0.4mmol, potassium acetate 6mmol, Isosorbide-5-Nitrae-dioxane 90mL are added in reaction flask, then vacuumize to system, the guarantor of nitrogen It protects, reacts 18 hours, after reaction, extract, revolving at 105 DEG C, column chromatography (eluant, eluent: n-hexane/methylene chloride=2: 1), it is recrystallized to give product B10, yield 68%.4. obtaining final product j by Suzuki (Suzuki) coupling reaction: will B101mmol, the step 2 products therefrom, that is, bromo- 10- of 9- (4- cyano) benzene anthracene 0.84mmol, catalyst four (triphenyl) phosphine palladium 0.12mmol, toluene 60mL, ethyl alcohol 20mL, K2CO333.6mmol (uses 20mL distilled water wiring solution-forming), is added to reaction flask, Under the protection of nitrogen, flow back for 24 hours at 110 DEG C.Methanol hot wash, suction filtration, re crystallization from toluene, distillation are finally produced after reaction Object.Yield 69%.Molecular formula is C50H35NO3, theoretical value 697.26, actual value 697.
Embodiment 13
With embodiment 12.(only need to by step 3 2. in the iodo- 4,6- dimethoxy -5- hydrogen substituted benzene of the chloro- 3- of 1- replace For iodo- 4, the 6- dimethyl -5- hydrogen substituted benzene of the chloro- 3- of 1-, then below step in the involved functional group for needing to be replaced It is replaced accordingly.) synthesis final product be k.
Embodiment 14
With embodiment 12.(only need to by step 3 2. in the iodo- 4,6- dimethoxy -5- hydrogen substituted benzene of the chloro- 3- of 1- replace For iodo- 4, the 6- dialdehyde-based -5- hydrogen substituted benzene of the chloro- 3- of 1-, then below step in the involved functional group for needing to be replaced It is replaced accordingly.) synthesis final product be l.
Embodiment 15
With embodiment 12.(only need to by step 3 2. in the iodo- 4,6- dimethoxy -5- hydrogen substituted benzene of the chloro- 3- of 1- replace For iodo- 4, the 6- dicyano -5- hydrogen substituted benzene of the chloro- 3- of 1-, then below step in the involved functional group for needing to be replaced It is replaced accordingly.) synthesis final product be m.
Embodiment 16
In steps 1 and 2 and step 3 1. with embodiment 3.(only need to by step 3 2. in the iodo- 4,5,6- of the chloro- 3- of 1- Three hydrogen substituted benzenes replace with iodo- 4,5,6- trimethoxy substituted benzene of the chloro- 3- of 1-, then involved in following step to need to be replaced The functional group changed is also replaced accordingly.) synthesis final product be n.
Embodiment 17
In steps 1 and 2 and step 3 1. with embodiment 3.(only need to by step 3 2. in the iodo- 4,5,6- of the chloro- 3- of 1- Three hydrogen substituted benzenes replace with iodo- 4,5,6- trimethyl substituted benzene of the chloro- 3- of 1-, then involved in following step to need to be replaced Functional group be also replaced accordingly.) synthesis final product be o.
Embodiment 18
In steps 1 and 2 and step 3 1. with embodiment 3.(only need to by step 3 2. in the iodo- 4,5,6- of the chloro- 3- of 1- Three hydrogen substituted benzenes replace with iodo- 4,5,6- trifluoro substituted benzene of the chloro- 3- of 1-, then below step in involved need to be replaced Functional group is also replaced accordingly.) synthesis final product be p.
Above-described embodiment is only the synthesis step of part of compounds, R in compound in the present invention1、R2、R3、R4It can be table Any one in 1, corresponding any combination；Work as R1When different, the 4- that the group of donor properties is synthesized in step 1, which powers, to be replaced Power supply in phenyl boric acid replaces difference, can be CH3、OCH3、C2H5、OC2H5Or C (CH3)3Any one of；Work as R2When different, The 4- that the group of electrophilic characteristic is synthesized in step 2 inhales electricity and replaces the suction electricity substitution in phenyl boric acid different, can be F, CF3、CN Any one of with CHO；Work as R3Or R4When different, for the 2. chloro- 3- of 1- iodo- 4 that the in step 3 walks, in 5,6- trisubstituted benzenes Three replace difference, and substituent group is R3、R4, R3And R4For any one of group of neutral group or donor properties or inhale Any one of group of characteristic electron, R3And R4It can be H or CH3、OCH3、C2H5、OC2H5、C(CH3)3、F、CF3, CN and Any one of CHO.
After tested, the thermogravimetric map of the target product a of above-described embodiment 1-3 is as shown in Fig. 3, can obtain from thermogravimetric map The thermal decomposition temperature of a is 438 DEG C out, illustrates that material a has good thermal stability.
After tested, the target product a of above-described embodiment 1-3 is respectively in hexamethylene, toluene and 1,2- dichloroethane solution (~10-6mol L-1) and UV absorption and fluorescence emission spectrum on film: Fig. 4 and Fig. 5 has made from embodiment 1-3 respectively Machine blue fluorescent material is the Absorption and emission spectra in different solutions；Fig. 6 is respectively organic blue made from embodiment 1-3 Absorption (square) and transmitting (circle) spectrum of the fluorescent material in film: as can be drawn from Figure 4, suction of a in different solvents Receiving peak is respectively 354/374/396,357/377/398,358/378/399nm, these peaks are from the characteristic absorption of anthracene Peak.It does not change a lot from the polarity of solvent is ascending, illustrates that the dipole moment of molecule ground state varies less.It can from Fig. 5 To obtain, emission peak of a in different solvents is respectively 418,425,427nm, wherein the increase with solvent polarity has red shift Phenomenon, and acromion gradually weakens, due in excitation state intramolecular dipole moment variation.As can be drawn from Figure 6, the suction of a It receives and emission peak is respectively the characteristic absorption and emission peak that these peaks 362/383/405,440nm are from anthracene.
Application examples 1
The preparation of organic electroluminescence device 1
The present embodiment prepares organic electroluminescence device 1 by the following method:
A) it cleans ITO (tin indium oxide) glass: using dish washing liquid, deionized water, THF, isopropanol solvent ultrasonic cleaning respectively Ito glass is distinguished 20 minutes, then handles 10 minutes in plasma cleaner, and sheet resistance is 15-20 Ω/sq；
B) the vacuum evaporation hole transmission layer NPB on anode ito glass, with a thickness of 30nm；
C) the vacuum evaporation electronic barrier layer TCTA on hole transmission layer NPB, with a thickness of 10nm.
D) on electronic barrier layer TCTA, vacuum evaporation luminescent layer compound a, with a thickness of 20nm；
E) on luminescent layer, TPBi of the vacuum evaporation as electron transfer layer, with a thickness of 40nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, with a thickness of 1nm；
G) on electron injecting layer, vacuum evaporation cathode Al, with a thickness of 100nm.
The structure of organic electroluminescence device 1 be successively lamination ITO (110nm) */NPB (30nm)/TCTA (10nm)/ EML:[a(20nm)]/TPBi(40nm)/LiF(1nm)/Al(100nm)。
Wherein material molecule structural formula used in device 1 (luminescent layer is compound a) is as shown in table 2 below:
Material molecule structural formula used in 2 device 1 of table
After tested, shine (EL) map, Current density-voltage-brightness (Cd-V-L) graphs, the electric current of device 1 are close Degree-current efficiency (Cd-CE-PE), current density-external quantum efficiency (Cd-EQE) graphs respectively such as Fig. 7, Fig. 8, figure 9, shown in Figure 10: as can be drawn from Figure 7: device 1 comes from shining for material m, and spectrum is not under different current densities Become, illustrates that its electroluminescent spectrum has good stability.As can be drawn from Figure 9, the maximum current efficiency of device 1 is 4.02Cd/A is obtained from Fig. 9,10: the efficiency roll-off very little of device 1 illustrates that device efficiency stability is good.
The photoelectric properties parameter of device 1 is as shown in table 3 below
The photoelectric parameter of 3 electroluminescent device 1 of table
In upper table, [a] device name, [b] luminescent layer, [c] represents ignition voltage, and [d] represents maximum current efficiency, [e] Maximum power efficiency is represented, [f] represents maximum external quantum efficiency, and [g] represents the maximum internal quantum effect in 500cd/A Rate, [h] represent excitation purity coordinate (CIE).
Organic assembly ignition voltage based on material of the present invention is 3.6V, and the y value of chromaticity coordinate CIE is 0.14, is realized The undoped dark blue OLED device of low voltage drive.Organic luminescent device of the invention can be used Electrophtography photosensor, It is the light sources such as flat-panel screens, duplicator, printer, LCD backlight source, timer and various luminescent devices, various aobvious Show device, various marks, various sensors, various doorplates etc..
Materials synthesis step prepared by the present invention is simple, at low cost, yield is high, the features such as being easily purified, in solution or thin Strong navy blue fluorescent emission is all presented under membrane stage.Material prepared by the present invention is applied in OLED device, and depth is realized Blue emission, maximum EQE is up to 3.66%.Material prepared by the present invention has in fields such as organic display, organic solid-state illuminations Certain application value and market prospects.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of organic blue fluorescent material of D-A type, it is characterised in that: its structural formula is as follows:
Wherein: R1The group of confession under directions characteristic electron, R2Refer to the group of electrophilic characteristic, R3、R4Refer to neutral group, donor properties The group of group or electrophilic characteristic.
2. the organic blue fluorescent material of a kind of D-A type according to claim 1, it is characterised in that: wherein R1For CH3、 OCH3、C2H5、OC2H5Or C (CH3)3；R2For F, CF3, CN or CHO；R3、R4For H, CH3、OCH3、C2H5、OC2H5、C(CH3)3、F、 CF3, CN or CHO.
3. a kind of preparation method of the organic blue fluorescent material of D-A type, it is characterised in that: using substance B and the bromo- 10- of 9-, (4- inhales Electronics replace) benzene anthracene carry out Suzuki coupling reaction be made, the substance B be 3- [10- (substitution of 4- supplied for electronic) benzene anthracene] -4,5,6- Trisubstituted benzene borate；Wherein the electrophilic in the bromo- 10- of 9- (4- electrophilic substitution) benzene anthracene is substituted by F, CF3, in CN or CHO It is any；Supplied for electronic is substituted by CH in 3- [10- (substitution of 4- supplied for electronic) benzene anthracene] -4,5,6- trisubstituted benzene borate3、OCH3、 C2H5、OC2H5Or C (CH3)3Any one of, the substituent group in 4,5,6- trisubstituted benzene borates is neutral group, supplied for electronic Any one of group of characteristic or any one of the group of electrophilic characteristic, neutral group are H；The group of donor properties Including CH3、OCH3、C2H5、OC2H5With C (CH3)3；The group of electrophilic characteristic includes F, CF3, CN and CHO.
4. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 3, it is characterised in that: substance B It is to be made by substance A by acid esterification, substance A is that 3- [10- (substitution of 4- supplied for electronic) benzene anthracene] -4,5,6- tri- replaces chlorine Benzene；Specific steps include: by 0.5~2mmol of substance A, 1.5~6mmol of connection boric acid pinacol ester, acid chloride 0.05~ 0.2mmol, 2- dicyclohexylphosphontetrafluoroborate -2 ', 6 ' -0.1~0.4mmol of dimethoxy-biphenyl, 1.5~6mmol of potassium acetate and Isosorbide-5-Nitrae-two Six 25~90mL of ring of oxygen mixing, after vacuumizing to system under the protection of nitrogen, reacts 12~18 hours at 95~105 DEG C, After reaction, it extracts, revolving, column chromatography is recrystallized to give substance B.
5. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 4, it is characterised in that: substance A It is to carry out Suzuki coupling reaction by 9- (4- power supply substituted-phenyl) -10 borate anthracenes and the iodo- 4,5,6- trisubstituted benzene of the chloro- 3- of 1- Obtain, specific steps include: by 9- (4- power substituted-phenyl) -10 borate anthracenes, the chloro- 3- of 1- iodo- 4,5,6- trisubstituted benzenes, Tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3Solution presses (1~3) mmol:(1~3) mmol:(0.1~0.3) mmol:(40 ~120) mL:(10~30) mL:(40~120) mmol mixing, under nitrogen protection, after 100~110 DEG C are reacted 12~24 hours Intermediate product is obtained, intermediate product is extracted, is rotated, column chromatography is recrystallized to give substance A.
6. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 5, it is characterised in that: 9- (4- Power substituted-phenyl) -10 borate anthracenes are made by the bromo- 10- of 9- (4- power supply replace) benzene anthracene acid esterification, specifically include following step It is rapid: by the bromo- 10- of the 9- of 4.22~12.66mmol (4- power supply replace) benzene anthracene, the isopropyl oxygen borate of 6.32~18.96mmol, After the THF mixing of 50~150mL, under the protection of nitrogen, it is small to react 8~12 at room temperature for the n-BuLi of 7.2~21.6mmol When, it after reaction, extracts, revolving, column chromatography, is recrystallized to give 9- (4- power supply substituted-phenyl) -10 borate anthracenes.
7. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 6, it is characterised in that: 9- is bromo- 10- (4- power supply replaces) benzene anthracene is to be obtained by 9- (4- power supply replaces) benzene anthracene by bromination, and specific steps include: by 9- (4- power supply replaces) benzene anthracene, N- bromo-succinimide and N,N-dimethylformamide presses (2.5~10) mmol:(3~12) Mmol:(40~150) mL mixing, under nitrogen gas ambient conditions, 85~90 DEG C are reacted 1~2 hour, and methanol is washed and filtered Obtain the bromo- 10- of 9- (4- power supply replaces)；
9- (4- power supply replaces), benzene anthracene was that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: by 9- Bromine anthracene, 4- power supply replace phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5~30) Mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, in atmosphere of inert gases item Under part, 100~110 DEG C after back flow reaction 12~24 hours by extraction, revolving, column chromatography, being recrystallized to give 9-, (4- power supply takes Generation) benzene anthracene.
8. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 3, it is characterised in that: 9- is bromo- 10- (4- inhales electricity and replaces) benzene anthracene is to be obtained by 9- (4- inhales electricity and replaces) benzene anthracene by bromination, and specific steps include: by 9- (4- inhales electricity and replaces) benzene anthracene, N- bromo-succinimide and N,N-dimethylformamide presses (2.5~10) mmol:(3~12) Mmol:(40~150) mL mixing, under the conditions of atmosphere of inert gases, 85~90 DEG C are reacted 1~2 hour, and methanol washing reaction produces Object, suction filtration obtain the bromo- 10- of 9- (4- inhales electricity and replaces) benzene anthracene；
9- (4- inhales electricity and replaces) benzene anthracene is that 9- bromine anthracene is obtained by Suzuki coupling reaction, and specific preparation step includes: by 9- Bromine anthracene, 4- inhale electric substituent group phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3According to (5~20) mmol:(7.5~ 30) mmol:(0.25~1) mmol:(50~200) mL:(15~60) mL:(50~200) mmol mixing, under nitrogen atmosphere, 100~110 DEG C back flow reaction 12~24 hours, after reaction, extract, revolving, column chromatography, be recrystallized to give 9- (4- inhale electricity Replace) benzene anthracene.
9. a kind of preparation method of the organic blue fluorescent material of D-A type according to claim 3, it is characterised in that: Suzuki In coupling reaction, it is additionally added catalyst, solvent and activator；Wherein, the bromo- 10- of substance B, 9- (4- electrophilic substitution) benzene anthracene, Ratio between catalyst, toluene, ethyl alcohol and activator is (0.25~1) mmol:(0.21~0.84) mmol:(0.03~ 0.12) mmol:(15~60) mL:(5~20) mmol:(8.4~33.6) mmol；Catalyst uses tetrakis triphenylphosphine palladium；It is living Agent uses K2CO3Solution；Suzuki coupling reaction, be under nitrogen gas ambient conditions, at 100~110 DEG C, reaction 12~ 24 hours, after reaction, methanol hot wash filtered, re crystallization from toluene, and distillation obtains final product.
10. a kind of a kind of organic blue fluorescent material of D-A type described in claim 1 is in organic electroluminescent diode apparatus Application.
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