CN106045977A - Bipolar blue phosphorescent host material based on carbazole and 1,2,4-triazole - Google Patents

Bipolar blue phosphorescent host material based on carbazole and 1,2,4-triazole Download PDF

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CN106045977A
CN106045977A CN201610376594.5A CN201610376594A CN106045977A CN 106045977 A CN106045977 A CN 106045977A CN 201610376594 A CN201610376594 A CN 201610376594A CN 106045977 A CN106045977 A CN 106045977A
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blue phosphorescent
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carbazole
phosphorescent material
triazole
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CN106045977B (en
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许慧侠
孙鹏
王科翔
杨婷婷
苗艳勤
王�华
许并社
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Taiyuan University of Technology
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Abstract

The invention discloses a bipolar blue phosphorescent host material which is as shown in a structural general formula (I) and takes carbazole and 1,2,4-triazole as a donor and a receptor respectively. The triplet-state energy level of the host material is improved by introducing an alkyl chain into the portion between carbazole and 1,2,4-triazole to prevent a conjugated structure between the donor and the receptor. When the bipolar blue phosphorescent host material is applied to dark blue phosphorescent organic electroluminescence devices, energy return between a host and a guest in the blue phosphorescent devices can be effectively prevented, and the luminous efficiency of the devices is improved. Please see the formula in the description.

Description

A kind of bipolarity blue phosphorescent material of main part based on carbazole and 1,2,4-triazole
Technical field
The present invention relates to phosphorescent light body material, particularly relating to a kind of is to, acceptor groups, energy with carbazole and triazole The phosphorescent light body material of enough blue light-emittings.
Background technology
Phosphorescent organic electroluminescent device (PhOLED:Phosphorescent organic-light emitting Devices) in display and solid-state illumination field, there is huge application prospect.But, compare with other materials, blue phosphorescent master The shortage of body material the most seriously constrains the development of its industrialization.The reason causing this situation essentially consists in: the bluest The triplet of phosphorescent light body material is not high enough, and the energy passback of object to main body reduces the efficiency of device；On the other hand The carrier transmission performance of blue phosphorescent material of main part is the best, and electronics and hole-recombination probability are low, and device efficiency declines；Finally, Heat stability and the film forming stability of material of main part are poor.
Following requirement should be met: 1 when selecting blue phosphorescent material of main part) the highest of blue phosphorescent host material molecules account for There are orbital energy level (HOMO) and lowest unoccupied molecular orbital energy level (LUMO) to match with the successive functional layers in device, the most just have It is beneficial to hole and electronics injects, thus reduce driving voltage；2) there is higher triplet, so can ensure main body Energy transmission between material and blue phosphorescent guest materials is exothermic process, and object does not has energy to return to material of main part；3) Good heat stability and film forming characteristics；4) good charge transport properties, makes electronics and hole can effectively answer in luminescent layer Close.
Bipolarity blue phosphorescent material of main part is the optimum selection solving these problems.Carbazole is blue phosphorescent material of main part In conventional functional group, owing to carbazole has less conjugated system, the lone pair electrons in its atom N can be effectively reduced The singletstate of molecule and triplet division, the triplet of carbazole group can reach 3.02eV, and therefore carbazole is carrying While high material of main part three line energy level, also there is the hole transporting properties of excellence.1,2,4-triazole is electron withdraw group, can Receive electronics by electronic induction effect, play the effect of transmission electronics；Meanwhile, the introducing of this group the most also may be used To improve the heat stability of material of main part.
Unfortunately, if by carbazole and 1,2,4-triazole groups are by having the chemical group of conjugated structure even Pick up and form bipolar host material, the triplet of material of main part will certainly be reduced, and Subjective and Objective material cannot be stoped Between energy passback, cause the efficiency of luminescent device to reduce.Such as: Joo Hyun Kim etc. (Synth. Met. 2007, 157,743) material of main part 9-{3-[5-(the 4-tert-butyl group-benzene has been synthesized with the 1,3,4-triazole of 9-phenyl carbazole and phenyl Base)-4-phenyl-4H-[1,2,4] triazole-3-yl]-phenyl }-9H-carbazole, its triplet is only in 2.82eV, and literary composition There is no relevant device data；W.-Y. Hung etc. (J. Mater. Chem., 2012,22,5410 5418) synthesize with Phenyl carbazole and bipolar host material 9-that 1,2,4-triazole is transport group (4-(3,5-diphenyl-1H-1,2,4-triazole- 1-yl) phenyl) triplet of-9H-carbazole is also only 2.82eV, and the maximum emission peak in dichloromethane is positioned at 427nm Place.
Document above report is to the triplet state energy of the bipolar host material of, acceptor groups based on carbazole and triazole Level is not the most the highest, it is impossible to meeting the demand of navy blue phosphorescent OLED device, it is all logical for being primarily due to its donor carbazole Crossing what pi-conjugated group and receptor triazole coupled together, this pi-conjugated group reduces the triplet of material of main part.
Summary of the invention
It is an object of the invention to provide a kind of is to the bipolarity blue phosphorescent master of/receptor with carbazole and 1,2,4-triazole Body material, by the conjugated structure between introducing alkyl chain stops to receptor between carbazole and 1,2,4-triazoles, main to improve The triplet of body material, stops the energy passback between host-guest in blue-light device.
Bipolarity blue phosphorescent material of main part based on carbazole and 1,2,4-triazole provided by the present invention has following General structure shown in formula I:
Wherein: R1For the straight or branched alkylidene that carbon number is 1～10, R2For hydrogen or aryl carbazole base.
As a kind of general synthetic method, the alkyl chain carbazole that can use bromination is donor monomer, spreading out of triazole Biology is by body unit, both is coupled together by Suzuki reaction, prepares said structure and lead to the bipolarity shown in formula I Blue phosphorescent material of main part.
Further, described Suzuki reaction is by donor monomer and to be existed according to the mol ratio of 1: 1～1.5 by body unit Back flow reaction 20～24h in toluene solution, obtain described target product.
Further, after the present invention is the target product dichloromethane extraction that will obtain, on a silica gel column with oil Ether: dichloromethane=5～8: 1 eluent carry out column chromatography for separation purification, obtain final blue phosphorescent material of main part.
Using said method of the present invention, the yield of the bipolarity blue phosphorescent material of main part prepared is more than 70%.
The bipolarity blue phosphorescent material of main part that the present invention prepares is mainly used in prepares organic electroluminescence device.
It is to, the blue phosphorescent main body material of receptor structure that the present invention has synthesized a class based on carbazole and 1,2,4-triazole Material, and by introducing alkyl chain, by described giving, acceptor groups couples together.The introducing of alkyl chain, has interrupted being total to of molecular structure Yoke, improve material of main part triplet (E T ), synthesis blue phosphorescent material of main partE T All at about 3.0eV, can Effectively to stop in blue phosphorescent device the energy passback between Subjective and Objective, apply in navy blue phosphorescent devices, it is possible to increase device The luminous efficiency of part.
On the other hand, the present invention uses alkyl chain by 1,2,4-triazoles of the carbazole of hole transport ability Yu electron-transporting After coupling together, the flexible alkyl chains of introducing effectively improves material of main part dissolubility in organic solvent, prepares for wet method Blue-light device provides possibility.
The blue phosphorescent material of main part of present invention synthesis has the wider optical band gap of about 3.5eV, its HOMO/LUMO energy Level can be good at being included the HOMO/LUMO of guest materials, thus realization body transmits to object energy completely, with Prepare high efficiency blue phosphorescent device.
It is special that blue phosphorescent material of main part synthesized by the present invention shows preferable current-voltage in single charge carrier device Property, show that it has preferable double carriers transmission characteristic.
The blue phosphorescent material of main part of present invention synthesis has preferable heat stability, its heat decomposition temperature (weightless 5% Temperature) 330～380 DEG C, the requirement of vacuum thermal evaporation can be met.
Accompanying drawing explanation
Fig. 1 is that the blue phosphorescent material of main part PPHCz of embodiment 1 preparation is at toluene, dichloromethane and tetrahydrofuran solution In uv absorption, fluorescence emission spectrum and antenna effect spectrum in 2-methyltetrahydrofuran solution.
Fig. 2 is the thermogravimetric curve of the PPHCz of embodiment 1 preparation.
Fig. 3 is the PPHCz of embodiment 1 preparation cyclic voltammetry curve in dichloromethane solution.
Fig. 4 is the voltage-current density curve of single charge carrier device based on PPHCz.
Fig. 5 is the electroluminescent spectrum of the blue PhOLED device with PPHCz as material of main part.
Fig. 6 is the Current density-voltage-brightness curve of the blue PhOLED device with PPHCz as material of main part.
Fig. 7 is that the current efficiency-electric current density-power efficiency of the blue PhOLED device with PPHCz as material of main part is bent Line.
Fig. 8 is the blue phosphorescent material of main part PPBCz uv absorption in dichloromethane solution/glimmering of embodiment 2 preparation Optical emission spectroscopy and the emission spectrum of PPBCz pressed powder.
Fig. 9 is the blue phosphorescent material of main part PPECz uv absorption in dichloromethane solution/glimmering of embodiment 3 preparation Optical emission spectroscopy.
Figure 10 is the blue phosphorescent material of main part PTPCz of embodiment 4 preparation fluorescence emission in dichloromethane solution Spectrum.
Detailed description of the invention
Following embodiment is only the preferred technical solution of the present invention, is not used to the present invention is carried out any restriction.For For those skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, made Any modification, equivalent substitution and improvement etc., should be included within the scope of the present invention.
Embodiment 1
2-cyanopyridine (5.21g, 50mmol), hydrazine hydrate (2.50g, 50mmol), 25mL ethanol, it is added sequentially to 250mL two In mouth round-bottomed flask, 0 DEG C of low-temp reaction 8h, generate the faint yellow pastel of thickness, ambient temperature in vacuum removes unnecessary ethanol, with A small amount of ether washing solid, filters, and room temperature in vacuo is dried 3h, obtains (2-pyridine) amidrazone white crystal.
(2-pyridine) amidrazone (4.08g, 30mmol), Na2CO3(3.15g, 30mmol), Benzenecarbonyl chloride. (4.20g, 30mmol), 30mL oxolane, add in two mouthfuls of round-bottomed flasks of 250mL, room temperature reaction 6h, filters.Much filtrate is in 30ml second two Back flow reaction 30min dehydration ring closure in alcohol, filter, be vacuum dried 8h, ethyl alcohol recrystallization, obtain 2-(3-phenyl-1H-1,2,4-tri- Azoles-5-base) pyridine white needle-like crystals, productivity 92%.
Carbazole (5.0g, 30mmol), 1,6-dibromo-hexane (36.0g, 150mmol), tetrabutyl ammonium bromide (TBAB) (1.0g, 3mmol), 40mL toluene, 50%KOH solution (25mL), it is sequentially added in two mouthfuls of round-bottomed flasks of 250mL, under nitrogen protection Back flow reaction 12h.Be cooled to room temperature, add 50mL deionized water, extract (50 × 3mL) with dichloromethane, organic layer spend from Sub-water washs repeatedly, and anhydrous magnesium sulfate is dried, and filters, decompression distillation, and crude product column chromatography for separation purifies (petroleum ether: dichloromethane Alkane=8: 1), obtain 9-(6-bromine hexyl)-9H-carbazole white crystal, productivity 78%.
1H NMR δ: 8.11 (dt, 2H, J=7.8 Hz, 1.2 Hz), 7.47-7.44 (m, 2H), 7.40 (d, 2H, J=8.4 Hz), 7.24-7.21 (m, 2H), 4.31 (t, 2H, J=7.2 Hz), 3.35 (t, 2H, J=7.2 Hz), 1.92-1.78 (m, 2H), 1.50-1.37 (m, 2H).
2-(3-phenyl-1H-1,2,4-triazole-5-bases) pyridine (2.21g, 10mmol), 9-(6-bromine hexyl)-9H-carbazole (3.96g, 12mmol), TBAB (0.32g, 1mmol), 30mL toluene, 50%KOH solution (15mL), it is sequentially added into 250mL two mouthfuls In round-bottomed flask, nitrogen is protected, and 30min, heating reflux reaction 24h are stirred at room temperature.It is cooled to room temperature, adds 50mL deionization Water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, and anhydrous magnesium sulfate is dried, and filters, decompression Distillation, crude product column chromatography for separation purify (petroleum ether: dichloromethane=5: 1), obtain 9-(6-(3-phenyl-5-(pyridine-2-base)- 1H-1,2,4-triazol-1-yls) hexyl)-9H-carbazole (PPHCz) white crystal, productivity 80%.
1H NMR (600 MHz, CDCl3) δ 8.52 (ddd, J1=4.8, J2=1.8, 0.9 Hz, 1H), 8.30 (dt, J1 = 7.9, J2=1.1 Hz, 1H), 8.18-8.15 (m, 2H), 8.10 (ddd, J = 7.8, J2=1.2, J3=0.7 Hz, 2H), 7.82 (td, J = 7.8, J2=1.8 Hz, 1H), 7.47-7.42 (m, 4H), 7.42- 7.39 (m, 1H), 7.37 (dt, J = 8.2, J2=0.9 Hz, 2H), 7.29 (ddd, J = 7.6, J2=4.8, J3=1.2 Hz, 1H), 7.22 (ddd, J = 7.9, J2=7.0, J3=1.0 Hz, 2H), 4.87-4.81 (m, 2H), 4.28 (t, J = 7.2 Hz, 2H), 2.00-1.83 (m, 4H), 1.43 (dd, J = 6.6, J2=3.0 Hz, 4H)。
13C NMR (600 MHz, CDCl3): δ 29.17, 32.98, 45.83, 53.66, 111.50, 121.56, 123.22, 125.75, 126.80, 128.32, 129.21, 131.42, 131.91, 134.16, 139.78, 143.32, 151.70, 155.12, 163.59。
FT-IR (KBr, cm-1): 3416, 3049, 2926, 2825, 1590, 1466, 1322, 1227, 1153, 1128, 1015, 920, 846, 793, 723。
Anal. Calcd for C31H29N5 (%): C, 78.95; H, 6.20; N, 14.85; found: C, 79.60; H, 6.10; N, 14.62。
The structural formula of prepared PPHCz is as follows.
Fig. 1 gives above-mentioned PPHCz ultraviolet in the solvent of dichloromethane, oxolane and three kinds of opposed polarities of toluene Absorb and fluorescence emission spectra.From figure 1 it appears that the emission peak of PPHCz is positioned at 351,368 and 390nm, at three kinds of solvents In the peak shape of Absorption and emission spectra and peak-peak position all do not change, show PPHCz intramolecular do not exist to, Charge transfer transition between receptor, it is pi-conjugated that the introducing of alkyl chain can interrupt between, receptor well.
In 2-methyltetrahydrofuran solution, test the antenna effect spectrum after PPHCz postpones 1ms, obtain shown in Fig. 1 The antenna effect curve of spectrum, and thus draw PPHCz triplet (E T ) it is 3.01eV.And the blue guest phosphorus of classics Luminescent material double (4,6-difluorophenyl pyridinato-N, C2') pyridinecarboxylic close iridium (FIrpic) triplet be 2.65eV, The energy level difference of 0.36eV, it is sufficient to stop the passback of triplet energy state.
Fig. 2 gives the thermogravimetric curve of described PPHCz, weight-loss curve can show that the heat decomposition temperature of material is 330 DEG C (weightless temperature) corresponding to 5%.
Fig. 3 gives the electrochemistry cyclic voltammetry curve of PPHCz in dichloromethane solution.The PPHCz obtained by test Beginning oxidation peak 1.6V, being calculated HOMO energy level is-6.00eV；By the uv absorption of PPHCz in dichloromethane solution with send out The cross point of light spectrum, can obtain further its optical band gap (Eg) it is 3.57eV, so its lumo energy is-2.43eV.By This understands PPHCz and has wider band gap, provides theoretical foundation for preparation OLED.
And then, the present embodiment is prepared for single charge carrier device of PPHCz respectively, special to verify the carrier transport of PPHCz Property.Its device architecture is respectively as follows: single hole device ITO/ NPB (20nm)/PPHCz (30nm)/NPB (20nm)/Al (200nm)；Single-electron device ITO/ TPBi (20nm)/PPHCz (30nm)/TPBi (20nm)/LiF (1nm)/Al (200nm).Wherein indium tin oxide ITO is anode, N, N-diphenyl-N, N-two (1-naphthyls)-1,1-biphenyl-4,4-two Amine (NPB) is hole transmission layer, and 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBi) is electric transmission and hole Barrier layer, lithium fluoride (LiF) and aluminum (Al) are composite cathode.The voltage-current density that Fig. 4 gives single charge carrier device is bent Line, it can be seen that single electron and single hole device are respectively provided with preferable electric current and voltage commutation characteristic, show that this material has double Carrier transmission characteristics.
In order to verify that can PPHCz be used as blue phosphorescent material of main part further, having made structure is ITO/ NPB (30nm)/ TCTA (10nm)/ PPHCz:Firpic 8%wt (30nm)/ TPBi (35nm)/ LiF (1nm)/ Al (200nm) device, device efficient lighting area 3 × 3mm.Fig. 5 gives device electroluminescent spectrum under different voltages, Maximum electroluminescent peak is positioned at 470,496nm, consistent with the photoluminescence spectra of Firpic, shows that device achieves material of main part Total energy to guest materials transmits, and does not has energy to return.
Fig. 6 gives the Current density-voltage-luminance test curve of above-mentioned blue-light device, curve understand device Big brightness is 3328cd/m2。
Fig. 7 gives with PPHCz as material of main part, and Firpic is the electric current effect of the blue phosphorescent device of guest emitting material Rate-electric current density-power efficiency curve, can show that from figure the maximum current efficiency of device is 11.5cd/A, peak power Efficiency is 7.6lm/W.
Embodiment 2
Carbazole (5.0g, 30mmol), 1,6-dibromobutane (31.9g, 150mmol), TBAB (1.0g, 3mmol), 40mL toluene, 50%KOH solution (25mL), is sequentially added in two mouthfuls of round-bottomed flasks of 250mL, lower back flow reaction 12h of nitrogen protection.It is cooled to room Temperature, adds 50mL deionized water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, anhydrous slufuric acid Magnesium is dried, and filters, decompression distillation, and crude product column chromatography for separation purifies (petroleum ether: dichloromethane=8: 1), obtains 9-(6-bromine fourth Base)-9H-carbazole (L3) white crystal, productivity 80%.
1H NMR δ: 8.13 (dt, 2H, J=7.8 Hz, 1.2 Hz), 7.48-7.47 (m, 2H), 7.42 (d, 2H, J=8.4 Hz), 7.26-7.24m, 2H), 4.35 (d, 2H, J=7.2 Hz), 3.36 (d, 1H, J=7.2 Hz), 1.96-1.80 (m, 1H), 1.52-1.39 (m, 1H).
2-(3-phenyl-1H-1,2,4-triazole-5-bases) pyridine (2.21g, 10mmol), 9-(6-brombutyl)-9H-carbazole (3.61g, 12mmol), TBAB (0.32g, 1mmol), 30mL toluene, 50%KOH solution (15mL), it is sequentially added into 250mL two mouthfuls In round-bottomed flask, nitrogen is protected, and 30min, heating reflux reaction 24h are stirred at room temperature.It is cooled to room temperature, adds 50mL deionization Water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, and anhydrous magnesium sulfate is dried, and filters, decompression Distillation, crude product column chromatography for separation purify (petroleum ether: dichloromethane=5: 1), obtain 9-(6-(3-phenyl-5-(pyridine-2-base)- 1H-1,2,4-triazol-1-yls) butyl)-9H-carbazole (PPBCz) white crystal, productivity 85%.
1H NMR (600 MHz, CDCl3) δ 8.54 (ddd, J1=4.8, J2=1.8, 0.9 Hz, 1H), 8.35 (dt, J1 = 7.9, J2=1.1 Hz, 1H), 8.19-8.16 (m, 2H), 8.13 (ddd, J = 7.8, J2=1.2, J3=0.7 Hz, 2H), 7.84 (td, J = 7.8, J2=1.8 Hz, 1H), 7.48-7.42 (m, 4H), 7.46- 7.40 (m, 1H), 7.39 (dt, J = 8.2, J2=0.9 Hz, 2H), 7.30(ddd, J = 7.6, J2=4.8, J3 =1.2 Hz, 1H), 7.25 (ddd, J = 7.9, J2=7.0, J3=1.0 Hz, 2H), 4.86-4.80 (m, 2H), 4.26 (t, J = 7.2 Hz, 2H), 2.02-1.85 (m, 2H), 1.44 (dd, J = 6.6, J2=3.0 Hz, 2H)。
Anal. Calcd for C29H25N5 (%): C, 78.53; H, 5.68; N, 15.79; found: C, 78.60; H, 5.49; N, 15.70。
The structural formula of prepared PPBCz is as follows.
Fig. 8 gives PPBCz uv absorption in methylene chloride, fluorescence emission spectrum and PPBCz pressed powder Fluorescence emission spectrum.Its absworption peak is predominantly located at 263,293,330, at 344nm, and emission peak is positioned at 348, at 366nm.Gu The emission peak of body powder is then predominantly located at 374,410, at 436nm, be respectively positioned on deep blue region.
Embodiment 3
Carbazole (5.0g, 30mmol), 1,6-Bromofume (27.8g, 150mmol), TBAB (1.0g, 3mmol), 40mL toluene, 50%KOH solution (25mL), is sequentially added in two mouthfuls of round-bottomed flasks of 250mL, lower back flow reaction 12h of nitrogen protection.It is cooled to room Temperature, adds 50mL deionized water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, anhydrous slufuric acid Magnesium is dried, and filters, decompression distillation, and crude product column chromatography for separation purifies (petroleum ether: dichloromethane=8: 1), obtains 9-(6-bromine second Base)-9H-carbazole white crystal, productivity 85%.
2-(3-phenyl-1H-1,2,4-triazole-5-bases) pyridine (2.21g, 10mmol), 9-(6-bromoethyl)-9H-carbazole (2.22g, 12mmol), TBAB (0.32g, 1mmol), 30mL toluene, 50%KOH solution (15mL), it is sequentially added into 250mL two mouthfuls In round-bottomed flask, nitrogen is protected, and 30min, heating reflux reaction 24h are stirred at room temperature.It is cooled to room temperature, adds 50mL deionization Water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, and anhydrous magnesium sulfate is dried, and filters, decompression Distillation, crude product column chromatography for separation purify (petroleum ether: dichloromethane=5: 1), obtain 9-(6-(3-phenyl-5-(pyridine-2-base)- 1H-1,2,4-triazol-1-yls) ethyl)-9H-carbazole (PPECz) white crystal, productivity 83%.
1H NMR (600 MHz, CDCl3) δ 8.52 (ddd, J1=4.8, J2=1.8, 0.9 Hz, 1H), 8.30 (dt, J1 = 7.9, J2=1.1 Hz, 1H), 8.18-8.15 (m, 2H), 8.10 (ddd, J = 7.8, J2=1.2, J3=0.7 Hz, 2H), 7.82 (td, J = 7.8, J2=1.8 Hz, 1H), 7.47-7.42 (m, 4H), 7.42- 7.39 (m, 1H), 7.37 (dt, J = 8.2, J2=0.9 Hz, 2H), 7.29 (ddd, J = 7.6, J2=4.8, J3=1.2 Hz, 1H), 7.22 (ddd, J = 7.9, J2=7.0, J3=1.0 Hz, 2H), 4.87-4.81 (m, 1H), 4.28 (t, J = 7.2 Hz, 1H), 2.00-1.83 (m, 1H), 1.43 (dd, J = 6.6, J2=3.0 Hz, 1H)。
Anal. Calcd for C27H21N5 (%): C, 78.05; H, 5.09; N, 16.86; found: C, 77.90; H, 5.12; N, 16.74。
The structural formula of prepared PPECz is as follows.
Fig. 9 provides PPECz uv absorption in dichloromethane solvent and fluorescence emission spectrum, the main position of its absworption peak In 260, at 292,332,340nm, and emission peak is positioned at 350, at 368nm.
Embodiment 4
(2-pyridine) amidrazone (4.08g, 30mmol), Na2CO3(3.15g, 30mmol), 4-bromo-benzoyl chloride (6.57g, 30mmol), 30mL oxolane, add in two mouthfuls of round-bottomed flasks of 250mL, room temperature reaction 6h, filters.Much filtrate is in 30ml second two Back flow reaction 30min dehydration ring closure in alcohol, filter, be vacuum dried 8h, ethyl alcohol recrystallization, obtain 2-(3-(4-bromophenyl)-1H-1, 2,4-triazole-5-bases) pyridine white needle-like crystals, productivity 80%.
2-(3-(4-bromophenyl)-1H-1,2,4-triazole-5-bases) pyridine (3.01g, 10mmol), 9-(6-bromine hexyl)- 9H-carbazole (3.32g, 10mmol), 1,10-Phen (0.827g, 0.148mmol), Hydro-Giene (Water Science). (3.9g, 2.0mmol), Cesium carbonate (6.7g, 20.65mmol), 40mL DMF, the lower heating reflux reaction 18h of nitrogen protection.Reaction knot Being cooled to room temperature after bundle, add 50mL deionized water, extract (50 × 3mL) with dichloromethane, organic layer is washed with deionized Repeatedly, anhydrous magnesium sulfate is dried, and filters, decompression distillation, and crude product column chromatography for separation purifies (petroleum ether: dichloromethane=5: 1), Obtain 9-(6-(3-(4-bromophenyl)-5-(pyridine-2-yl)-1H-1,2,4-triazol-1-yls) hexyl) 8H-carbazole white solid, Productivity 83%.
9-(6-(3-(4-bromophenyl)-5-(pyridine-2-yl)-1H-1,2,4-triazol-1-yl) hexyl) 8H-carbazole (2.75g, 5mmol), 9-(4-(4,4,5,5-tetramethyl-1,3-dioxy boron ring-2-base) phenyl)-9H-carbazole (2.77g, 7.5mmol), tetrakis triphenylphosphine palladium (115.6mg, 0.1mmol), sodium carbonate (2mol/L, 7.5mL), 40mL toluene, 20mL second Alcohol, is sequentially added in two mouthfuls of round-bottomed flasks of 250mL, the lower heating reflux reaction 24h of nitrogen protection.Reaction is cooled to room after terminating Temperature, adds 50mL deionized water, extracts (50 × 3mL) with dichloromethane, and organic layer is washed with deionized repeatedly, anhydrous slufuric acid Magnesium is dried, and filters, decompression distillation, and crude product column chromatography for separation purifies (petroleum ether: dichloromethane=5: 1), obtains 9-(4'-(1-benzene Base-5-(pyridine-2-base)-1H-1,2,4-triazole-3-base)-[1,1'-biphenyl]-4-base)-9H-carbazole (PTPCz) white crystalline substance Body, productivity 75%.
Figure 10 is PTPCz fluorescence emission spectrum in dichloromethane solution, and its maximum emission peak is positioned at 369nm, for deeply Blue light emitting region.

Claims (5)

1. one kind based on carbazole and 1, the bipolarity blue phosphorescent material of main part of 2,4-triazoles, has shown in following formula I General structure:
Wherein: R1For the straight or branched alkylidene that carbon number is 1～10, R2For hydrogen or aryl carbazole base.
2. the synthetic method of bipolarity blue phosphorescent material of main part described in claim 1, is that the alkyl chain carbazole using bromination is Donor monomer, the derivant of triazole is by body unit, by Suzuki reaction prepare shown in described general structure (I) bipolar Property blue phosphorescent material of main part.
The synthetic method of bipolarity blue phosphorescent material of main part the most according to claim 1, is characterized in that donor monomer Target product is obtained according to mol ratio back flow reaction 20～24h in toluene solution of 1: 1～1.5 with by body unit.
The synthetic method of bipolarity blue phosphorescent material of main part the most according to claim 2, is characterized in that the mesh that will obtain After mark product extracts with dichloromethane, on a silica gel column with petroleum ether: dichloromethane=5～8: 1 eluent carry out column chromatography and divide From purification, obtain blue phosphorescent material of main part.
5. bipolarity blue phosphorescent material of main part described in claim 1 is in the application prepared on organic electroluminescence device.
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CN106939000A (en) * 2017-02-13 2017-07-11 太原理工大学 Hot activation delayed fluorescence material based on 1,2,4 triazole acceptors

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CN106905295A (en) * 2017-02-13 2017-06-30 太原理工大学 Navy blue fluorescent material based on 1,2,4 triazole derivatives and preparation method thereof
CN106939000A (en) * 2017-02-13 2017-07-11 太原理工大学 Hot activation delayed fluorescence material based on 1,2,4 triazole acceptors
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