CN108383693A - A kind of organic blue fluorescent material and its preparation method and application - Google Patents
A kind of organic blue fluorescent material and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of organic blue fluorescent material and its preparation method and application, the structural formula such as following formula (I) of such material, wherein R includes the group of donor properties or the group of electrophilic characteristic.Its preparation process includes mainly：Suzuki coupling reactions are carried out using 9 benzene anthracene, 10 borate and 1,4 dibromo, 2,5 disubstituted benzenes, and organic blue fluorescent material is made.The present invention passes through the sophisticated design to material molecule, two anthracene mulecular luminescence units are connected using benzene as pi-conjugated bridge chain, steric group is imported in the contraposition of central pi-conjugated bridge chain phenyl ring to eliminate the interaction of the π pi accumulations between molecule, the thermal stability and high luminous quantum efficiency that the organic blue fluorescent material prepared has had.
Description
Technical field
The present invention relates to organic electroluminescent LED fields, and in particular to a kind of organic blue fluorescent material and its preparation
Methods and applications.
Background technology
Organic electroluminescent LED (Organic Light-Emitting Diodes, OLED), because its is all solid state, oneself
Shine, wide viewing angle, low voltage drive, can be flexible the features such as, it is considered to be most having for next generation's display and solid-state lighting field is competing
Strive the technology of power.By nearly effort in 30 years, OLED achieves considerable in brightness, efficiency, service life, stability etc.
Progress, while industrialization prospect also makes first appearance.Restricting current OLED mainly has following without complete commercialized key factor
Two：First is price problem, and the yields of OLED line is relatively low at present, and the cost of manufacture of vacuum evaporation process is still
Far above liquid crystal display (LCD)；Second is the life problems of blue phosphor materials, and phosphor material has high luminous efficiency, but
Phosphor material generally requires heavy metal coordination, and synthesis is difficult, of high cost, and the service life is bad, especially blue phosphor materials these
Defect is never resolved.Compared with phosphor material, blue fluorescent material does not need expensive heavy metal coordination, synthesis letter
Single, at low cost, the service life is good, with its replace blue phosphor materials made of OLED with better commercial application prospect.Due to indigo plant
The energy gap of light itself is bigger, therefore blue emission is difficult to generate high efficiency, and thus efficient blue light directly influences business
The production of change.
Invention content
It is an object of the invention to overcome problems of the prior art, provide a kind of organic blue fluorescent material and its
Preparation method and application, the thermal stability and high luminous quantum efficiency that prepared material has had are applied to dark blue OLED
When device, performance is good, external quantum efficiency (EQE) is high.
In order to achieve the above object, material of the invention adopts the following technical scheme that：
Its structural formula is as follows：
Wherein R includes the group of donor properties or the group of electrophilic characteristic.
Further, the group of donor properties includes CH3、C2H5、OCH3Or OC2H5；The group of electrophilic characteristic includes
F、CF3, CN or CHO.
The technical solution of preparation method of the present invention is：Include the following steps：Using -10 borate of 9- benzene anthracene and 1,4- bis-
Bromo- 2,5- disubstituted benzenes carry out Suzuki coupling reactions and organic blue fluorescent material are made.
Further, -10 borate of 9- benzene anthracene is obtained by the bromo- 10 benzene anthracene acid esterifications of 9-, and specific steps include：
The bromo- 10 benzene anthracenes of 9-, isopropyl oxygen borate, n-BuLi and THF are pressed into (1.4~2.8) g：(1.34~2.67) g：(0.42~
0.81)g：(30~56) mL is mixed, and is reacted at room temperature under the conditions of atmosphere of inert gases, and purification after reaction obtains 9- benzene anthracene-
10 borates.
Further, n-BuLi is added at -78 DEG C；
The bromo- 10 benzene anthracenes of 9- are that 9- benzene anthracene brominations obtain, and specific preparation process includes：By 9- benzene anthracene, N- bromo succinyl
Imines and N,N-dimethylformamide press (2.15~4.29) g：(1.8~3.6) g：(100~200) mL is mixed, in inert gas
Under ambient conditions, 85~90 DEG C are reacted 1~2 hour, and purification obtains the bromo- 10 benzene anthracenes of 9-.
Further, 9- benzene anthracene is that 9- bromines anthracene is obtained by Suzuki coupling reactions, and specific preparation process includes：By 9-
Bromine anthracene, phenyl boric acid, tetrakis triphenylphosphine palladium, toluene, ethyl alcohol and K2CO3By (2.60~5.14) g：(1.83~3.66) g：(0.58
~1.16) g：(100~200) mL：(30~60) mL：(13.82~27.64) g is mixed, under the conditions of atmosphere of inert gases, 100
~110 DEG C reaction 12~24 hours after purification obtain 9- benzene anthracenes.
Further, bromo- 2, the 5- disubstituted benzenes of Isosorbide-5-Nitrae-two are bromo- 2, the 5- of bromo- 2, the 5- dimethyl benzenes of Isosorbide-5-Nitrae-two, Isosorbide-5-Nitrae-two bis-
Ethylo benzene, bis- bromo- 2,5- dimethoxy benzenes of 1,4-, bis- bromo- 2,5- diethoxybenzenes of 1,4-, bis- bromo- 2,5- difluorobenzenes of 1,4-, 1,
Bis- bromo- 2,5- dialdehyde-baseds benzene of bis- bromo- 2,5- of 4-, bis- trifluoromethylbenzenes, bis- bromo- 2,5- dicyanobenzenes of 1,4- or 1,4-.
Further, in Suzuki coupling reactions, catalyst, solvent and activator solution have been additionally added, wherein 9- benzene
Ratio between -10 borate of anthracene, bis- bromo- 2,5- disubstituted benzenes of 1,4-, catalyst, solvent and activator is (5~10) mmol：
(1~2) mmol：(0.2~0.4) mmol：(40~75) mL：(16.5~33) mmol；
Suzuki coupling reactions are under nitrogen gas ambient conditions, and at a temperature of 100~110 DEG C, reaction 12~24 is small
When.
Further, catalyst uses tetrakis triphenylphosphine palladium；Solvent is molten using the mixing of toluene and homogeneous solvent ethyl alcohol
Agent；Activator uses K2CO3, activator solution is the solid K of 16.5~33mmol2CO3It is dissolved in 8~15mL distilled water and obtaining
's.
Application of organic blue fluorescent material in organic electroluminescent LED part as described above.
Compared with prior art, the present invention has technique effect beneficial below：
The organic fluorescence materials of the present invention are anthracene derivatives, can emit navy blue fluorescence.In order to eliminate organic molecule
Between strong pi-pi accumulation and the Fluorescence quenching effect that brings, have supplied for electronic special by being introduced on the pi-conjugated bridge chain phenyl ring at center
Property group or electrophilic characteristic group, restrained effectively intermolecular pi-pi accumulation, improve material luminescent quantum effect
Rate.Materials synthesis prepared by the present invention is simple, yield is high, is easily purified, and two are connected as pi-conjugated bridge chain by using benzene
Anthracene molecule realizes blue emission as luminescence unit；By importing space steric hindrance group in the contraposition of central pi-conjugated bridge chain phenyl ring
It interacts to eliminate the pi-pi accumulation between molecule, realizes high luminous quantum efficiency；It applies in OLED, performance is good.Using
Such material is as luminescent material：1) in undoped device, the blue-light device of high-definition television standard (HDTV), energy are realized
Cost of manufacture is reduced, production technology is simplified；2) in the doping device of material based on CBP, efficient HDTV standards are realized
Dark blue luminescent device；3) in the material (guest materials based on such material：DSA-Ph it in doping device), realizes efficiently
Sky blue luminescent device.In short, the present invention is on the bridge phenyl ring of material molecule by introducing space steric hindrance group, to inhibit point
Pi-pi accumulation between son improves the quantum production efficiency of material.The blue light of high-definition television standard (HDTV) is realized in OLED
Device, device performance are good.
In the preparation method of the present invention, it is single as shining two anthracene molecules to be connected as pi-conjugated bridge chain by using benzene
Member, while space steric hindrance group is imported to eliminate the pi-pi accumulation phase interaction between molecule in the contraposition of central pi-conjugated bridge chain phenyl ring
With being successfully prepared out organic blue fluorescent material of high thermal stability, high luminous quantum efficiency.
Material prepared by the present invention has the characteristics that synthesis cost is low, yield is high, is easily purified, under ultraviolet light,
Strong navy blue fluorescent emission is all presented in solution or film.Such material is applied in OLED, and high-definition television standard is realized
(HDTV) dark blue transmitting, EQE (8.6%) are far above conventional fluorescent material (5%), the organic luminescent device point of material of the present invention
Bright voltage is in 3~3.4V.
Description of the drawings
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 nuclear magnetic spectrum of organic blue fluorescent material made from the embodiment of the present invention 4.
Fig. 4 is the mass-spectrogram of organic blue fluorescent material made from the embodiment of the present invention 4.
Fig. 5 is the thermogravimetric collection of illustrative plates of anthracene derivative a and b made from 1-6 of the embodiment of the present invention.
Fig. 6 is absorption spectrum of organic blue fluorescent material in toluene solution made from the embodiment of the present invention 1 and 4.
Fig. 7 is emission spectrum of organic blue fluorescent material in toluene solution made from the embodiment of the present invention 1 and 4.
Fig. 8 is absorption spectrum of organic blue fluorescent material on film made from the embodiment of the present invention 1 and 4.
Fig. 9 is emission spectrum of organic blue fluorescent material on film made from the embodiment of the present invention 1 and 4.
(EL) collection of illustrative plates that shines that Figure 10 is device 1-3 produced by the present invention.
Figure 11 is Current density-voltage-brightness (Cd-V-L) graphs of device 1-3 produced by the present invention.
Figure 12 is the graphs of current density-external quantum efficiency (Cd-EQE) of device 1-3 produced by the present invention.
Specific implementation mode
The present invention connects two anthracene mulecular luminescences by the sophisticated design to material molecule using benzene as pi-conjugated bridge chain
Unit imports steric group to eliminate the interaction of the pi-pi accumulation between molecule, system in the contraposition of central pi-conjugated bridge chain phenyl ring
The thermal stability and high luminous quantum efficiency having had for the organic blue fluorescent material gone out.Its chemical structural formula is as follows.
Wherein R refers to the group of donor properties or the group of electrophilic characteristic, preferably CH3、C2H5、OCH3、OC2H5Or F,
CF3, CN, CHO, chemical structural formula is as follows：
The specific synthetic route of organic blue fluorescent material of the present invention is as follows：
(1) by taking the synthesis of compound a as an example, specific synthetic route is shown below：
(2) synthesis of compound b, specific synthetic route are shown below：
1. by 9- bromines 2.60~5.14g of anthracene, 1.83~3.66g of phenyl boric acid, 30~60mL of solution of potassium carbonate, toluene 100~
200mL, 30~60mL of ethyl alcohol are added to reaction bulb, wherein solution of potassium carbonate be 13.82~27.64g potassium carbonate is added 30~
It is matched in 60mL water；It is eventually adding 0.58~1.16g tetrakis triphenylphosphine palladiums.Then system is vacuumized, nitrogen protection
Under, it flows back 12~24 hours at 100~110 DEG C.After reaction, it extracts, revolving, column chromatography is recrystallized to give product.
2. the bromination of 9- benzene anthracenes：By 9- benzene 2.15~4.29g of anthracene, n,N-Dimethylformamide (DMF) 100~200mL, N-
Bromo-succinimide (NBS) 1.8~3.6g is added to reaction bulb, is then vacuumized to system, under nitrogen protection, 85~90 DEG C
Reaction 1~2 hour.Methanol washs, and suction filtration obtains product.
3. the acid esterification of the bromo- 10 benzene anthracenes of 9-：By bromo- 10 benzene, the 1.40~2.80g of anthracene of 9-, isopropyl oxygen borate 1.34~
2.67g, 0.42~0.81g of n-BuLi (are added) at -78 DEG C, and 30~56mL of THF are added to reaction bulb, then to system
It vacuumizes, under the protection of nitrogen, stirs 8~12 hours at room temperature.After reaction, it extracts, revolving, column chromatography recrystallizes
To product.
4. the synthesis of final product：By -10 bis- bromo- 2,5- disubstituted benzenes 1 of borate 5~10mmol, 1,4- of 9- benzene anthracene~
2mmol, catalyst four (triphenyl) phosphine 0.2~0.4mmol of palladium, 30~60mL of toluene, ethyl alcohol 10~15mL, K2CO316.5~
33mmol (with 8~15mL distilled water wiring solution-forming), is added to reaction bulb, under the protection of nitrogen, the reflux 12 at 100~110 DEG C
~for 24 hours.After reaction, methanol hot wash, suction filtration, re crystallization from toluene, distillation obtain final product.
Wherein, bromo- 2, the 5- disubstituted benzenes of Isosorbide-5-Nitrae-two are bromo- 2, the 5- dimethyl benzenes of Isosorbide-5-Nitrae-two, bromo- 2, the 5- diethyl of Isosorbide-5-Nitrae-two
Benzene, bis- bromo- 2,5- difluorobenzenes of bis- bromo- 2,5- dimethoxy benzenes of 1,4-, bis- bromo- 2,5- diethoxybenzenes of 1,4- or 1,4-, 1,4-
Two bromo- 2,5-, bis- trifluoromethylbenzenes, bis- bromo- 2,5- dicyanobenzenes of 1,4-, bis- bromo- 2,5- dialdehyde-baseds benzene of 1,4-.The carbonic acid of addition
Potassium solution is so that it is converted into active reaction intermediate in order to activate borate ion.It is to increase solvent to add ethyl alcohol
Hydrophily makes reaction be carried out under homogeneous phase condition.
The present invention is described in further details below by specific embodiment.
Embodiment 1
1. 9- bromines anthracene 2.60g, phenyl boric acid 1.83g, potassium carbonate 13.82g (to be added 30mL distilled water, it is molten to be made into 2.0M
Liquid), toluene 100mL, ethyl alcohol 30mL is added to reaction bulb, adds 0.58g tetrakis triphenylphosphine palladiums.Then system is taken out true
Sky, under nitrogen protection, 100 DEG C are flowed back 12 hours.After reaction, toluene extraction, revolving, column chromatography (eluent：Just oneself
Alkane), recrystallization (n-hexane/toluene=4:1) product is obtained.Yield 86%.
2. the bromination of 9- benzene anthracenes：9- benzene anthracene 2.15g, DMF 100mL, NBS 1.80g are added to reaction bulb, then to body
System vacuumizes, and reacts 1 hour for 85 DEG C under nitrogen protection.After reaction, methanol washs, and suction filtration obtains bromo- 10 benzene of product 9-
Anthracene.Yield 85%.
3. the bromo- 10 benzene anthracene acid esterifications of 9-：By the bromo- 10 benzene anthracene 1.40g of 9-, isopropyl oxygen borate 1.34g, n-BuLi
0.42g (is added) at -78 DEG C, and THF 30mL are added to reaction bulb, are vacuumized to system, is stirred at room temperature 8 hours.
After reaction, it extracts, column chromatography (eluent n-hexane/dichloromethane=1：1) (n-hexane/toluene=3, is recrystallized:1)
To -10 borate of product 9- benzene anthracene.Yield 55%.
4. obtaining final product a by Suzuki (Suzuki) coupling reaction：By -10 borate 6mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two
Bromo- 2,5- dimethyl benzenes 1mmol, tetrakis triphenylphosphine palladium 0.2mmol, toluene 30mL, ethyl alcohol 10mL, K2CO316.5mmoL (using
8mL water wiring solution-forming), it is added to reaction bulb, then system is vacuumized, is flowed back 12 hours under the protection of 100 DEG C of nitrogen.Instead
After answering, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product a.Yield 40%.Nuclear magnetic resonance spectroscopy：1HNMR
(400MHz, CDCl3) δ [ppm] 7.85 (d, J=8.02Hz, 4H), 7.76 (d, J=9.98Hz, 4H), 7.62 (dd, J=
8.90Hz, 4.50Hz, 4H), 7.57 (dd, J=8.80Hz, 4.26Hz, 4H) 7.55-7.36 (m, 10H), 7.40 (s, 2H),
1.98 (s, 6H), nuclear magnetic spectrum is illustrated in fig. 1 shown below.Mass spectrum (m/s), molecular formula C48H34, theoretical value 610.78, actual value
It is 611.40, mass-spectrogram is illustrated in fig. 2 shown below.
Embodiment 2
By 9- bromines anthracene 3.50g, phenyl boric acid 2.52g, potassium carbonate 18.82g (45mL water, wiring solution-forming is added), toluene
136mL, ethyl alcohol 45mL are added in reaction bulb, are eventually adding 0.82g tetrakis triphenylphosphine palladiums.System vacuumizes, nitrogen protection
It flows back 18 hours under the conditions of 105 DEG C.After reaction, toluene extraction, revolving, column chromatography (eluent：N-hexane), recrystallization
(n-hexane/toluene=4：1) product is obtained.Yield 86%.2. 9- benzene anthracene brominations：By 9- benzene anthracene 3.50g, DMF 130mL,
NBS2.94g is added to reaction bulb, is then vacuumized to system, under nitrogen protection 88 DEG C of reaction 1.5h.After reaction, first
Alcohol hot wash filters, and obtains the bromo- 10 benzene anthracenes of product 9-, yield 87%.3. the bromo- 10 benzene anthracene acid esterifications of 9-：By the bromo- 10 benzene anthracenes of 9-
2g, isopropyl oxygen borate 1.91g, n-BuLi 0.58g (being added at -78 DEG C), THF 45mL are added to reaction bulb, then right
System vacuumizes, and is stirred at room temperature 10 hours.After reaction, toluene extraction, revolving, column chromatography (eluent n-hexane/bis-
Chloromethanes=1：1) (n-hexane/toluene=3, is recrystallized:1) -10 borate products of 9- benzene anthracene, yield 63% are obtained.4. passing through
Suzuki coupling reactions obtain final product a：By -10 borate 9mmol of 9- benzene anthracene, bromo- 2, the 5- dimethyl benzenes of Isosorbide-5-Nitrae-two
1.5mmoL, tetrakis triphenylphosphine palladium 0.36mmol, toluene 40mL, ethyl alcohol 12mL, K2CO328mmol (is made into molten with 14mL water
Liquid), it is added to reaction bulb, then system is vacuumized, is flowed back 20 hours under the protection of 105 DEG C of nitrogen.After reaction, first
Alcohol hot wash suction filtration, re crystallization from toluene, distillation obtain final product a, yield 54%.Mass spectrum (m/s), theoretical value 610.78 are practical
Value is 611.4.
Embodiment 3
1. by 9- bromines anthracene 5.14g, phenyl boric acid 3.66g, potassium carbonate 27.64g (60mL water, wiring solution-forming is added), toluene
200mL, ethyl alcohol 60mL are added to reaction bulb, are eventually adding 1.16g tetrakis triphenylphosphine palladiums.Then system is vacuumized, in nitrogen
Lower 110 DEG C of gas shielded flows back 24 hours.After reaction, toluene extraction, revolving, column chromatography (eluent：N-hexane), recrystallization
(n-hexane/toluene=4：1) product is obtained.Yield 86%.2. 9- benzene anthracene brominations：By 9- benzene anthracene 4.29g, DMF 200mL, NBS
3.6g is added to reaction bulb, is then vacuumized to system, reacts 2 hours for 90 DEG C under nitrogen protection.After reaction, methanol heat
It washes, filter, obtain the bromo- 10 benzene anthracenes of product 9-, yield 77%.3. the bromo- 10 benzene anthracene acid esterifications of 9-：By the bromo- 10 benzene anthracenes of 9-
2.80g, isopropyl oxygen borate 2.67g, n-BuLi 0.81g (being added at -78 DEG C), THF 56mL are added to reaction bulb, so
System is vacuumized afterwards, is stirred at room temperature 12 hours.After reaction, toluene extraction, revolving, column chromatography (eluent just oneself
Alkane/dichloromethane=1：1) (n-hexane/toluene=3, is recrystallized:1) -10 borate products of 9- benzene anthracene, yield 77% are obtained.④
Final product a is obtained by Suzuki coupling reactions：By -10 borate 10mmol of 9- benzene anthracene, bromo- 2, the 5- dimethyl benzenes of Isosorbide-5-Nitrae-two
2mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 15mL, K2CO333mmoL (uses 15mL water wiring solution-forming),
It is added to reaction bulb.Then system is vacuumized, is flowed back 24 hours under the protection of 110 DEG C of nitrogen.After reaction, methanol heat
Wash suction filtration, re crystallization from toluene, distillation obtain final product a, yield 55%.Mass spectrum (m/s), theoretical value 610.78, actual value are
611.4。
Embodiment 4
Step is 1. to step 3. the same as embodiment 1.
4. obtaining final product b finally by Suzuki coupling reactions：By -10 borate 5mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two is bromo-
2,5- dimethoxy benzene 2mmol, four (triphenyl) phosphine palladium 0.4mmol, toluene 50mL, ethyl alcohol 15mL, K2CO333mmoL (is used
15mL water wiring solution-forming), it is added to reaction bulb, then system is vacuumized, is flowed back 12 hours under the protection of 100 DEG C of nitrogen.
After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product b, yield 43%.Nuclear magnetic resonance spectroscopy：1H
NMR (400MHz, CDCl3) δ [ppm] 7.95 (d, J=8.04Hz, 4H), 7.76 (d, J=8.26Hz, 4H), 7.70-7.57 (m,
10H), 7.50 (dd, J=8.90Hz, 6.40Hz, 4H), 7.4 (dd, J=8.70Hz, 6.40Hz, 4H), 7.16 (s, 2H), 3.58
(s, 6H), nuclear magnetic spectrum is illustrated in fig. 3 shown below.Mass spectrum (m/s), molecular formula C48H34O2Theoretical value is 642.26, and actual value is
642.4 mass-spectrogram is illustrated in fig. 4 shown below.
Embodiment 5
Step is 1. to step 3. the same as embodiment 2.
4. obtaining final product b finally by Suzuki coupling reactions：By -10 borate 9mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two is bromo-
2,5- dimethoxy benzene 1.5mmol, four (triphenyl) phosphine palladium 0.36mmol, toluene 36mL, ethyl alcohol 10mL, K2CO328mmol (is used
14mL water wiring solution-forming), it is added to reaction bulb, then system is vacuumized, is flowed back 20 hours under the protection of 105 DEG C of nitrogen.
After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product b, yield 55%.Mass spectrum (m/s), theoretical value
It is 642.26, actual value 642.4.
Embodiment 6
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product b finally by Suzuki coupling reactions：Wherein by -10 borate 10mmol of 9- benzene anthracene, Isosorbide-5-Nitrae -
Two bromo- 2,5- dimethoxy benzenes 2mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 15mL, K2CO3 33mmol
(using 15mL water wiring solution-forming), is added to reaction bulb, is then vacuumized to system, and reflux 24 is small under the protection of 110 DEG C of nitrogen
When.After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product b, yield 55%.Mass spectrum (m/s), it is theoretical
Value is 642.26, actual value 642.4.
Embodiment 7
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product c finally by Suzuki coupling reactions：Wherein by -10 borate 10mmol of 9- benzene anthracene, Isosorbide-5-Nitrae -
Two bromo- 2,5- diethoxybenzenes 2mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 15mL, K2CO3 33mmol
(using 15mL water wiring solution-forming), is added to reaction bulb, and it is small then to vacuumize the reflux 24 under the protection of 110 DEG C of nitrogen to system
When.After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product c, yield 46%.Mass spectrum (m/s), it is theoretical
Value is 670.29, actual value 669.8.
Embodiment 8
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product d finally by Suzuki coupling reactions：Wherein by -10 borate 9mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two
Bromo- 2,5- diethylbenzenes 1.5mmol, tetrakis triphenylphosphine palladium 0.36mmol, toluene 60mL, ethyl alcohol 15mL, K2CO333mmol,
(using 15mL water wiring solution-forming), is added to reaction bulb, and it is small then to vacuumize the reflux 24 under the protection of 110 DEG C of nitrogen to system
When.After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product d, yield 42%.Mass spectrum (m/s), it is theoretical
Value is 638.30, actual value 637.88.
Embodiment 9
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product e finally by Suzuki coupling reactions：Wherein by -10 borate 8mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two
Bromo- 2,5- difluorobenzenes 2mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 15mL, K2CO333mmol (uses 15mL
Water wiring solution-forming), it is added in reaction bulb, then system is vacuumized and is flowed back 24 hours under the protection of 110 DEG C of nitrogen.Instead
After answering, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product e, yield 44%.Mass spectrum (m/s), theoretical value are
618.71 actual value 616.86.
Embodiment 10
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product f finally by Suzuki coupling reactions：Wherein by -10 borate 6mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two
Bromo- 2,5- bis- benzotrifluoride 2mmol, tetrakis triphenylphosphine palladium 0.3mmol, toluene 40mL, ethyl alcohol 10mL, K2CO316.5mmol
(using 8mL water wiring solution-forming), is added to reaction bulb, then vacuumizes to system and flow back 24 hours under the protection of 110 DEG C of nitrogen.
After reaction, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product f, yield 45%.
Embodiment 11
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product g finally by Suzuki coupling reactions：Wherein by -10 borate 9mmol of 9- benzene anthracene, Isosorbide-5-Nitrae-two
Bromo- 2,5- dicyanobenzenes 1.5mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 60mL, K2CO333mmol (is used
15mL water wiring solution-forming), it is added to reaction bulb, then system is vacuumized and is flowed back 24 hours under the protection of 110 DEG C of nitrogen.Instead
After answering, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product g, yield 50%.
Embodiment 12
Step is 1. to step 3. the same as embodiment 3.
4. obtaining final product h finally by Suzuki coupling reactions：Wherein by -10 borate 10mmol of 9- benzene anthracene, Isosorbide-5-Nitrae -
Two bromo- 2,5- dialdehyde-baseds benzene 2mmol, tetrakis triphenylphosphine palladium 0.4mmol, toluene 60mL, ethyl alcohol 15mL, K2CO333mmol (is used
15mL water wiring solution-forming), it is added to reaction bulb, then system is vacuumized and is flowed back 24 hours under the protection of 110 DEG C of nitrogen.Instead
After answering, methanol hot wash suction filtration, re crystallization from toluene, distillation obtain final product h, yield 50%.
After tested, the thermogravimetric collection of illustrative plates of the target product a and b of above-described embodiment 1-6 are illustrated in fig. 5 shown below, can from thermogravimetric collection of illustrative plates
To show that the heat decomposition temperature of a and b are respectively 350 DEG C and 380 DEG C, illustrate that material a and b have good thermal stability.
After tested, the target product a and b of above-described embodiment 1-6 is respectively (~10 in toluene solution-6mol L-1) and it is thin
Ultra-violet absorption spectrum on film：Fig. 6 and Fig. 7 is respectively the Absorption and emission spectra in toluene solution；Fig. 8 and Fig. 9 are respectively thin
The Absorption and emission spectra of film：As can be drawn from Figure 6, the absorption peak of a and b is respectively 354/375/397nm, 354/375/
397nm, these peaks are from the characteristic absorption peak of anthracene.As can be drawn from Figure 7, the emission peak of a and b be respectively 411nm,
416nm, wherein b have Red Shift Phenomena relative to a, it may be possible to caused by the methoxy group imported has the pi-conjugated effects of p-.From
Fig. 8 can show that the absorption peak of a and b are respectively that these peaks 362/381/402nm, 362/380/402nm are from anthracene
Characteristic absorption peak.As can be drawn from Figure 9, the emission peak of a and b is respectively 427nm, 418nm a has Red Shift Phenomena relative to b, can
Can be caused by their crystal accumulation modes.
Application examples 1
The preparation of organic electroluminescence device 1
The present embodiment prepares organic electroluminescence device 1 by the following method：
14.a) clean ITO (tin indium oxide) glass：Deionized water, acetone, isopropanol is used to be cleaned by ultrasonic ito glass respectively
It 30 minutes respectively, is then handled 10 minutes in plasma cleaner, sheet resistance is 15-20 Ω/sq；
B) the vacuum evaporation hole transmission layer NPB on anode ito glass, thickness 40nm；
C) the vacuum evaporation hole blocking layer TCTA on hole transmission layer NPB, thickness 5nm.
D) on hole blocking layer TCTA, vacuum evaporation luminescent layer compound BD1-PMe, thickness 20nm；
E) on luminescent layer, the vacuum evaporation TPBi as electron transfer layer, thickness 40nm；
F) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness 1nm；
G) on electron injecting layer, vacuum evaporation cathode Al, thickness 100nm.
The structure of organic electroluminescence device 1 be successively lamination ITO (95nm) */NPB (40nm)/TCTA (5nm)/
EML:[BD1-PMe(20nm)]/TPBi(40nm)/LiF(1nm)/Al(100nm)。
Application examples 2
The preparation of organic electroluminescence device 2
The present embodiment prepares organic electroluminescence device 2 by the following method：
A) ITO (tin indium oxide) glass is cleaned：Deionized water, acetone, isopropanol is used to be cleaned by ultrasonic ito glass difference respectively
It 30 minutes, is then handled 10 minutes in plasma cleaner, sheet resistance is 15-20 Ω/sq；
B) the vacuum evaporation hole transmission layer TAPC on anode ito glass, thickness 50nm；
C) on hole transmission layer TAPC, vacuum evaporation luminescent layer compound BD1-PMe (5wt%)：CBP, thickness are
40nm；
D) on luminescent layer, the vacuum evaporation TmPyPB as electron transfer layer, thickness 40nm；
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness 1nm
F) on electron injecting layer, vacuum evaporation cathode Al, thickness 100nm.
The structure of organic electroluminescence device 2 is ITO (95nm) */TAPC (50nm)/EML of lamination setting successively:
[BD1-PMe (5%wt)：CBP(40nm)]/TmPyPB(40nm)/LiF(1nm)/Al(100nm).
Application examples 3
The preparation of organic electroluminescence device 3
The present embodiment prepares organic electroluminescence device 3 by the following method：
A) ITO (tin indium oxide) glass is cleaned：Deionized water, acetone, isopropanol is used to be cleaned by ultrasonic ito glass difference respectively
It 30 minutes, is then handled 10 minutes in plasma cleaner, sheet resistance is 15-20 Ω/sq；
B) the vacuum evaporation hole transmission layer TAPC on anode ito glass, thickness 50nm；
C) on hole transmission layer TAPC, vacuum evaporation luminescent layer DSA-Ph (3%wt)：BD1-PMe, thickness are
40nm；
D) on luminescent layer, the vacuum evaporation TmPyPB as electron transfer layer, thickness 40nm；
E) on electron transfer layer, vacuum evaporation electron injecting layer LiF, thickness 1nm
F) on electron injecting layer, vacuum evaporation cathode Al, thickness 100nm.
The structure of organic electroluminescence device 3 is ITO (95nm) */TAPC (50nm)/EML:[DSA-Ph (3%wt)：b
(40nm)]/TmPyPB(40nm)/LiF(1nm)/Al(100nm)。
Material molecule structural formula is as shown in table 1 below used in wherein device 1-3.
Material molecule structural formula used in 1 device 1-3 of table
After tested, shine (EL) collection of illustrative plates, Current density-voltage-brightness (Cd-V-L) graphs, the electric current of device 1-3
The graphs of density-external quantum efficiency (Cd-EQE) are respectively as shown in Figure 10, Figure 11, Figure 12：As can be drawn from Figure 10：Device
Part 1 and device 2 come from shining for material a, and device 3 comes from shining for guest materials DSA-Ph, confirmed material a not only
It can be used as material of main part, be also used as guest materials.As can be drawn from Figure 11：The highest current density of device 1, illustrates
Undoped device can also reach high efficiency, and the brightness of device 2 is maximum.It is obtained from Figure 12：The efficiency roll-off of device 1-3 is not
It is quickly, to illustrate that the stabilised efficiency of device is relatively good.
The photoelectric properties parameter of device 1-3 is as shown in table 2 below.
The photoelectric parameter of 2 electroluminescent device 1-3 of table
【a】Device name,【b】Luminescent layer,【c】Ignition voltage is represented,【d】Maximum power efficiency is represented,【e】Represent maximum
External quantum efficiency,【f】The maximum external quantum efficiency in 1000cd/A is represented,【g】Maximum brightness is represented,【h】Represent color
Purity coordinate (CIE).
The organic luminescent device ignition voltage of material of the present invention is in 3~3.4V, and excitation purity is obviously in navy blue region,
Y value is dark blue coloured light less than 0.1, shows the preparation for realizing the undoped device of navy blue.Device 3 shows such material not only
It can be used as guest materials, be also used as material of main part, therefore the present invention is upper very valuable in application.Organic hair of the present invention
Optical device can be used in Electrophtography photosensor, flat-panel screens, duplicator, printer, LCD backlight source, timer
Equal light sources and various luminescent devices, various display devices, various marks, various sensors, various doorplates etc..
Materials synthesis prepared by the present invention is at low cost, yield is high, the features such as being easily purified, under solution or filminess all
Strong navy blue fluorescent emission is presented.Material prepared by the present invention is applied in OLED device, and high-definition television mark is realized
The dark blue transmitting of accurate (HDTV), EQE>8.6%.Material prepared by the present invention is in fields such as organic display, organic solid-state illuminations
With certain application value and market prospects.
Claims (10)
1. a kind of organic blue fluorescent material, it is characterised in that：Its structural formula is as follows：
Wherein R includes the group of donor properties or the group of electrophilic characteristic.
2. organic blue fluorescent material according to claim 1, it is characterised in that：The group of donor properties includes CH3、
C2H5、OCH3Or OC2H5；The group of electrophilic characteristic includes F, CF3, CN or CHO.
3. a kind of preparation method of organic blue fluorescent material, it is characterised in that：Include the following steps：Using -10 boron of 9- benzene anthracene
Acid esters and bis- bromo- 2,5- disubstituted benzenes of 1,4- carry out Suzuki coupling reactions and organic blue fluorescent material are made.
4. the preparation method of organic blue fluorescent material according to claim 3, it is characterised in that：- 10 boric acid of 9- benzene anthracene
Ester is obtained by the bromo- 10 benzene anthracene acid esterifications of 9-, and specific steps include：By the bromo- 10 benzene anthracenes of 9-, isopropyl oxygen borate, just
Butyl lithium and THF press (1.4~2.8) g：(1.34~2.67) g：(0.42~0.81) g：(30~56) mL is mixed, in indifferent gas
It is reacted at room temperature under body ambient conditions, purification after reaction obtains -10 borate of 9- benzene anthracene.
5. the preparation method of organic blue fluorescent material according to claim 4, it is characterised in that：N-BuLi be -
It is added at 78 DEG C；
The bromo- 10 benzene anthracenes of 9- are that 9- benzene anthracene brominations obtain, and specific preparation process includes：By 9- benzene anthracene, N- bromo-succinimides
(2.15~4.29) g is pressed with N,N-dimethylformamide：(1.8~3.6) g：(100~200) mL is mixed, in atmosphere of inert gases
Under the conditions of, 85~90 DEG C are reacted 1~2 hour, and purification obtains the bromo- 10 benzene anthracenes of 9-.
6. the preparation method of organic blue fluorescent material according to claim 5, it is characterised in that：9- benzene anthracenes are 9- bromine anthracenes
It is obtained by Suzuki coupling reactions, specific preparation process includes：By 9- bromines anthracene, phenyl boric acid, tetrakis triphenylphosphine palladium, first
Benzene, ethyl alcohol and K2CO3By (2.60~5.14) g：(1.83~3.66) g：(0.58~1.16) g：(100~200) mL：(30~
60)mL：(13.82~27.64) g mix, under the conditions of atmosphere of inert gases, 100~110 DEG C reaction 12~24 hours after purify
Obtain 9- benzene anthracenes.
7. the preparation method of organic blue fluorescent material according to claim 3, it is characterised in that：Bis- bromo- 2,5- of 1,4-
Disubstituted benzenes are bis- bromo- 2,5- dimethyl benzenes of 1,4-, bis- bromo- 2,5- diethylbenzenes of 1,4-, bis- bromo- 2,5- dimethoxys of 1,4-
Benzene, bis- bromo- 2,5- diethoxybenzenes of 1,4-, bis- bromo- 2,5- difluorobenzenes of 1,4-, bis- bromo- 2,5- of 1,4-, bis- trifluoromethylbenzenes, 1,4-
Bis- bromo- 2,5- dialdehyde-baseds benzene of two bromo- 2,5- dicyanobenzenes or 1,4-.
8. the preparation method of organic blue fluorescent material according to claim 3, it is characterised in that：Suzuki coupling reactions
In, it has been additionally added catalyst, solvent and activator solution, wherein bromo- 2, the 5- bis- of -10 borate of 9- benzene anthracene, Isosorbide-5-Nitrae-two replaces
Ratio between benzene, catalyst, solvent and activator is (5~10) mmol：(1~2) mmol：(0.2~0.4) mmol：(40~
75)mL：(16.5~33) mmol；
Suzuki coupling reactions at a temperature of 100~110 DEG C, are reacted 12~24 hours under nitrogen gas ambient conditions.
9. the preparation method of organic blue fluorescent material according to claim 8, it is characterised in that：Catalyst uses four
(triphenylphosphine) palladium；Solvent uses the mixed solvent of toluene and homogeneous solvent ethyl alcohol；Activator uses K2CO3, activator solution is
The solid K of 16.5~33mmol2CO3It is dissolved in and obtaining in 8~15mL distilled water.
10. application of organic blue fluorescent material in organic electroluminescent LED part as described in claim 1.
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| CN109503427A (en) * | 2018-12-28 | 2019-03-22 | 陕西师范大学 | A kind of organic blue fluorescent material of D-A type and its preparation method and application |
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Application publication date: 20180810 |