CN103554114A - Disubstituted pyrene diquinoxaline derivative, and preparation method and application thereof and electroluminescent device - Google Patents

Disubstituted pyrene diquinoxaline derivative, and preparation method and application thereof and electroluminescent device Download PDF

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CN103554114A
CN103554114A CN201310477565.4A CN201310477565A CN103554114A CN 103554114 A CN103554114 A CN 103554114A CN 201310477565 A CN201310477565 A CN 201310477565A CN 103554114 A CN103554114 A CN 103554114A
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pyrene
tertiary butyl
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黄宏
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    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
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Abstract

The invention discloses a disubstituted pyrene diquinoxaline derivative, and a preparation method and application thereof and an electroluminescent device. The disubstituted pyrene diquinoxaline derivative has a structural general formula as below, wherein Ar is an aromatic group. The invention uses electron transport performance of the disubstituted pyrene diquinoxaline derivative to connect blue light emitting groups with relatively high quantum efficiency, so as to realize a more distorted molecular structure, reduce the intermolecular pi-pi stacking interaction and balance the luminescent layer cavity and electron transport rate, and further improve the luminescent efficiency of the device. The disubstituted pyrene diquinoxaline derivative involved in the invention is propitious to stability of the device and acquisition of excellent electroluminescent performance of the device, is conducive to the development of high-performance full-color display, and can be widely applied to the fields of OLED large screen display with high requirement on the brightness and OLED white-light illumination.

Description

Two replace pyrene two oxazoline derivates, preparation method, application and electroluminescent device
Technical field
The present invention relates to field of light emitting materials, relate in particular to a kind of two and replace pyrene two oxazoline derivates, preparation method, application and electroluminescent device.
Background technology
Organic Light Emitting Diode (OLED) is through the development of two more than ten years, increasing luminous organic material is developed, some groups that are applied at first blue light fluorescence luminescent material also obtain further perfect, such as anthracene, naphthalene, phenanthrene, pyrene and triple-lap alkene etc. has relatively wide bandwidth, all can meet well the requirement of blue light fluorescence luminescent material, its structural formula is as follows respectively:
From said structure formula, can find out, the groups such as anthracene, naphthalene, phenanthrene, pyrene and triple-lap alkene that are applied to blue light fluorescence luminescent material form by carbon hydrogen element, and its hole, electric transmission speed are relatively low, need further to be improved; Except triple-lap alkene, all the other each groups all have relatively planarity preferably, so its derivative is while being applied to fluorescent device luminescent layer, easily forms pi-pi accumulation, easily forms more excimer(excite state atom), cause luminous efficiency to decline.
Therefore, prior art has yet to be improved and developed.
Summary of the invention
In view of above-mentioned the deficiencies in the prior art, the object of the present invention is to provide two replacement pyrenes two oxazoline derivates, preparation method, application and electroluminescent device, be intended to solve the hole of existing blue light fluorescence luminescent material and electric transmission speed is lower, easily form pi-pi accumulation, easily form more excimer(excite state atom), problem that luminous efficiency is lower.
Technical scheme of the present invention is as follows:
Replace pyrene two oxazoline derivates, wherein, its general structure is as follows:
Figure 2013104775654100002DEST_PATH_IMAGE002
, wherein, Ar is aromatic group.
Two described replacement pyrene two oxazoline derivates, wherein, Ar is
Figure 2013104775654100002DEST_PATH_IMAGE003
,
Figure 2013104775654100002DEST_PATH_IMAGE004
,
Figure 2013104775654100002DEST_PATH_IMAGE005
,
Figure 2013104775654100002DEST_PATH_IMAGE006
or
Figure 2013104775654100002DEST_PATH_IMAGE007
.
As above two replace a preparation method for pyrene two oxazoline derivates, and wherein, it comprises step:
A, 2-tertiary butyl pyrene is dissolved in to CH 2cl 2in solution, and will contain BTMABr 3cH 2cl 2solution drips in mixed solution, and at room temperature nitrogen protection reaction 3 ~ 8h, after question response completes, adds the shrend reaction of going out, with dichloromethane extraction 3 ~ 5 times, merge organic phase, add anhydrous sodium sulfate drying, filter, the organic solvent of removing wherein obtains the 7-tertiary butyl-1,3-dibromo pyrene;
B, by the 7-tertiary butyl-1,3-dibromo pyrene is dissolved in the mixing solutions of methylene dichloride and Isosorbide-5-Nitrae-dioxy six alkane, stirs 30 min, under nitrogen protection, adds successively NaIO 4, H 2o and RuCl 3, at room temperature stir 15 ~ 20h, the black reaction liquid obtaining is poured in excessive frozen water solution, organic phase layering, uses dichloromethane extraction 3 ~ 5 times, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent evaporate to dryness wherein, its crude product is purified by chromatographic column and is obtained glassy yellow solid 1, the bromo-7-of 3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones;
Under C, nitrogen environment protection, add successively the bromo-7-of 1,3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones, O-Phenylene Diamine, add acetic acid to dissolve simultaneously, reflux 3 ~ 6h, question response liquid is cooled to room temperature, add the shrend reaction of going out, dichloromethane extraction 3 ~ 5 times for gained mixed solution, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent is wherein evaporated, the crude product obtaining is purified with flash chromatography column chromatography method, obtains the yellow solid 7-tertiary butyl-1,3-dibromo pyrene two quinolines;
D, by the 7-tertiary butyl-1 obtaining, 3-dibromo pyrene two quinolines, the boric acid that comprises aryl are dissolved in toluene solution, add wet chemical and dehydrated alcohol simultaneously, and add catalyst P d (PPh simultaneously 3) 4, in nitrogen environment, be heated to 70 ~ 180 ℃ of lucifuge reactions and reflux 3 ~ 48 hours; Then be cooled to room temperature, add water washing, with dichloromethane extraction, merge organic phase, anhydrous sodium sulfate drying, filters, and removes organic solvent, obtains white solid powder two replace pyrene two oxazoline derivates with column chromatography method.
Two described replacement pyrenes the preparation method of two oxazoline derivates, wherein, in described step D, the boric acid that comprises aryl is phenylo boric acid, 1-naphthalene boronic acids, 2-naphthalene boronic acids, 1-phenanthryl boric acid or 3-(9-phenyl carbazole) boric acid.
Two described replacement pyrenes the preparation method of two oxazoline derivates, wherein, in described steps A, 2-tertiary butyl pyrene, BTMABr 3and CH 2cl 2the molar mass of solvent is than 1:(2 ~ 4): (4 ~ 10).
Two described replacement pyrenes the preparation method of two oxazoline derivates, wherein, in described step B, the 7-tertiary butyl-1,3-dibromo pyrene, NaIO 4, H 2o and RuCl 3the molar mass of solvent is than being 1:(8 ~ 12): (8 ~ 10): (0.5 ~ 2.0).
Two described replacement pyrenes the preparation method of two oxazoline derivates, wherein, in described step C, the bromo-7-of 1,3-bis-tertiary butyl-4, the molar mass of 5,9,10-, tetra-pyrene quinones, O-Phenylene Diamine and acetic acid solvent is than being 1:(2 ~ 2.2): (8 ~ 10).
Two described replacement pyrenes the preparation method of two oxazoline derivates, wherein, in described step D, the 7-tertiary butyl-1,3-dibromo pyrene two quinolines, the boric acid that comprises aryl, salt of wormwood and catalyst P d (PPh 3) 4molar mass than for 1:(2 ~ 6): (5 ~ 50): (0.02 ~ 0.25).
As above two replace an application for pyrene two oxazoline derivates, wherein, are applied in electroluminescent device.
, wherein, the anode that described electroluminescent device stacks gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode; Described luminescent layer is comprised of above-mentioned two replacement pyrenes two oxazoline derivates.
Beneficial effect: provided by the invention two replace pyrene two oxazoline derivates, preparation method, application and electroluminescent device; two replacement pyrenes of the present invention two oxazoline derivates have hole, electric transmission speed relatively preferably; be connected with blue light fluorophor; can strengthen well the rigidity of whole compound; make the degreeof tortuosity of compound structure become large; can well strengthen compound vitreous conversion temp; strengthen the stability of luminescent device; while is pi-pi accumulation and the excimer of Fluorophotometry luminophor molecule preferably, improves luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the structural representation of device preferred embodiment of the present invention.
Fig. 2 is current density-current efficiency graph of a relation of device 4 in embodiments of the invention.
Fig. 3 is the electroluminescent spectrum figure of device 4 in embodiments of the invention.
Embodiment
The invention provides two replacement pyrenes two oxazoline derivates, preparation method, application and electroluminescent device, for making object of the present invention, technical scheme and effect clearer, clear and definite, below the present invention is described in more detail.Should be appreciated that specific embodiment described herein, only in order to explain the present invention, is not intended to limit the present invention.
Of the present invention two replace pyrene two oxazoline derivates, and its general structure is as follows:
Figure 204205DEST_PATH_IMAGE002
。
Wherein, Ar is aromatic group, for example:
When Ar is
Figure 121345DEST_PATH_IMAGE003
time, this compound (two replace pyrene two oxazoline derivates) is the 7-tertiary butyl-1,3-hexichol pyrene two quinolines (being abbreviated as DPhANPy);
When Ar is
Figure 901082DEST_PATH_IMAGE004
time, this compound is the 7-tertiary butyl-1,3-bis-(1-naphthyl) pyrene two quinolines (being abbreviated as 1-DNaANPy);
When Ar is
Figure 296292DEST_PATH_IMAGE005
time, this compound is the 7-tertiary butyl-1,3-bis-(2-naphthyl) pyrene two quinolines (being abbreviated as 2-DNaANPy);
When Ar is
Figure 110664DEST_PATH_IMAGE006
time, this compound is the 7-tertiary butyl-1,3-bis-(1-phenanthryl) pyrene two quinolines (being abbreviated as DPNANPy);
When Ar is
Figure 618612DEST_PATH_IMAGE007
time, this compound is the 7-tertiary butyl-1,3-bis-(3-(9-phenyl carbazole)) pyrene two quinolines (being abbreviated as DPhCzANPy);
Above-claimed cpd all contains different aromatic groups, should be different substituted radicals, and be respectively phenyl, 1-naphthyl, 2-naphthyl, 1-phenanthryl and 9-phenyl carbazole, this type of substituted radical be chromophore, further segmentation, this type of substituted radical all belongs to the blue light emitting group in chromophore.Connect different chromophores and can adjust well glow color and the rigidity intensity of compound, and above-claimed cpd all can be used as blue light fluorescence luminescent material.
Below the replacement pyrene of two in the present invention two oxazoline derivates preparation methods are described, its step is as follows:
Figure 2013104775654100002DEST_PATH_IMAGE008
from above-mentioned flow process, can find out, its reaction can be summarized as: first by pyrene bromination, next under strong oxidizer effect, be oxidized, with O-Phenylene Diamine effect formation dibromo pyrene two quinoline intermediates, then by Suzuki(suzuki reaction) two final replacement pyrene two oxazoline derivates of reaction formation.
Concrete reactions steps is as follows:
A, 2-tertiary butyl pyrene is dissolved in to CH 2cl 2in solution, and will contain BTMABr 3cH 2cl 2solution slowly drips in mixed solution by constant pressure funnel, at room temperature nitrogen protection reaction 3 ~ 8h, wherein, 2-tertiary butyl pyrene, BTMABr 3and CH 2cl 2the molar mass of solvent is than 1:(2 ~ 4): (4 ~ 10), after question response completes, add the shrend reaction of going out, with dichloromethane extraction 3 ~ 5 times, merge organic phase, add anhydrous sodium sulfate drying, filter, the organic solvent of removing wherein obtains the 7-tertiary butyl-1,3-dibromo pyrene;
B, by the 7-tertiary butyl-1,3-dibromo pyrene is dissolved in the mixing solutions of methylene dichloride and Isosorbide-5-Nitrae-dioxy six alkane (the two volume ratio is 1:1), stirs 30 min, under nitrogen protection, adds successively NaIO 4, H 2o and RuCl 3obtain black mixed solution, its black mixed solution at room temperature stirs 15 ~ 20 h and obtains black reaction liquid, the 7-tertiary butyl-1 wherein, 3-dibromo pyrene, NaIO 4, H 2o, and RuCl 3the molar mass of solvent is than 1:(8 ~ 12): (8 ~ 10): (0.5 ~ 2), black reaction liquid is directly poured in excessive frozen water solution into organic phase layering at once, with dichloromethane extraction 3 ~ 5 times, merge organic phase, add anhydrous magnesium sulfate drying, filter, to wherein solvent evaporate to dryness, its crude product directly with chromatographic column purify (methylene dichloride/hexane) glassy yellow solid 1, the bromo-7-of 3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones;
Under C, nitrogen environment protection, in dry round-bottomed flask, add successively 1; the bromo-7-of 3-bis-tertiary butyl-4; 5,9,10-, tetra-pyrene quinones, O-Phenylene Diamine; add acetic acid to dissolve simultaneously; wherein 1, the bromo-7-of 3-bis-tertiary butyl-4,5; the molar mass of 9,10-, tetra-pyrene quinones, O-Phenylene Diamine and acetic acid solvent is than 1:(2 ~ 2.2): (8 ~ 10).Reflux 3 ~ 6h, question response liquid is cooled to room temperature, add a large amount of shrends reaction of going out, dichloromethane extraction 3 ~ 5 times for gained mixed solution, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent is wherein evaporated, the crude product obtaining is purified with flash chromatography column chromatography method, obtain the yellow solid 7-tertiary butyl-1,3-dibromo pyrene two quinolines;
D, general be the resulting solid 7-tertiary butyl-1 above, and 3-dibromo pyrene two quinolines, the boric acid that comprises aryl are dissolved in toluene solution, add wet chemical and dehydrated alcohol simultaneously, and add catalyst P d (PPh simultaneously 3) 4, wherein, the 7-tertiary butyl-1,3-dibromo pyrene two quinolines, the boric acid that comprises aryl, salt of wormwood and catalyst P d (PPh 3) 4molar mass ratio be 1:(2 ~ 6): (5 ~ 50): (0.02 ~ 0.25), simultaneously toluene be (5 ~ 100) with the volume ratio of dehydrated alcohol: 1, in nitrogen environment, be heated to 70 ~ 180 ℃ of lucifuges and react backflow 3 ~ 48 hours; Then be cooled to room temperature, add water washing, dichloromethane extraction, merges organic phase, and anhydrous sodium sulfate drying filters, and removes organic solvent, with column chromatography method, obtains white solid powder, and of the present invention two replace pyrene two oxazoline derivates.
The preparation of particular compound is described respectively below:
Embodiment 1
The preparation of DPhANPy:
A, 2-tertiary butyl pyrene (1.0mmol) is dissolved in to CH 2cl 2in solution (25ml), and will be containing BTMABr 3(3.0mmol) CH 2cl 2(20ml) solution slowly drips in mixed solution by constant pressure funnel, and at room temperature nitrogen protection reaction 4h, after react, adds the shrend reaction of going out, use dichloromethane extraction 4 times.Productive rate: 90%, MS (APCI): theoretical value C 20h 16br 2: 414.0, experimental value, 415.2 (M+1) +.
B, by the 7-tertiary butyl-1,3-dibromo pyrene (2.4mmol) is dissolved in the mixing solutions of methylene dichloride (20ml) and Isosorbide-5-Nitrae-dioxy six alkane (20ml), stirs 30 min, under nitrogen protection, adds successively NaIO 4(20mmol), H 2o(25ml) and RuCl 3(1.5mmol), its black mixed solution at room temperature stirs 18 h, and black reaction liquid is directly poured in excessive frozen water solution, organic phase layering at once, uses dichloromethane extraction 5 times, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent evaporate to dryness wherein, its crude product directly with chromatographic column purify (methylene dichloride/hexane) glassy yellow solid 1, the bromo-7-of 3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones; Productive rate: 30%, MS (APCI): theoretical value C 20h 12br 2o 4: 473.9, experimental value, 474.8 (M+1) +.
C, under nitrogen environment protection, in dry round-bottomed flask, add successively 1, the bromo-7-of 3-bis-tertiary butyl-4, 5, 9, 10-tetra-pyrene quinones (0.17mmol), O-Phenylene Diamine (0.34mmol), add acetic acid (10ml) to dissolve simultaneously, reflux 5h, question response liquid is cooled to room temperature, add a large amount of shrends reaction of going out, dichloromethane extraction 4 times of gained mixed solution, merge organic phase, add anhydrous magnesium sulfate drying, filter, solvent is wherein evaporated, the crude product obtaining is purified with flash chromatography column chromatography method, obtain the yellow solid 7-tertiary butyl-1, 3-dibromo pyrene two quinolines, productive rate: 80%, MS (APCI): theoretical value C 32h 20br 2n 4: 618.0, experimental value, 620.3 (M+1) +.
D, general be the resulting solid 7-tertiary butyl-1 above, 3-dibromo pyrene two quinolines (5.0mmol), phenylo boric acid (10mmol) are dissolved in toluene solution, add wet chemical (2M) (20ml) and dehydrated alcohol (10ml) simultaneously, and add catalyst P d (PPh simultaneously 3) 4(0.25mmol), in nitrogen environment, being heated to 110 ℃ of lucifuge reactions refluxes 24 hours; Then be cooled to room temperature, add water washing, dichloromethane extraction, merges organic phase, and anhydrous sodium sulfate drying filters, and removes organic solvent, with column chromatography method, obtains white solid powder, i.e. the 7-tertiary butyl-1,3-hexichol pyrene two quinolines (DPhANPy); Productive rate 60%, MS (TOF): theoretical value C 44h 30n 4: 614.2470 (M+H) +, experimental value, 614.2455.
Embodiment 2
The preparation of 1-DNaANPy:
The preparation process of its preparation process and DPhANPy is similar, be in steps d with the preparation process difference of DPhANPy, the 1-naphthalene boronic acids of usining replaces phenylo boric acid as starting raw material, can make the 7-tertiary butyl-1,3-bis-(1-naphthyl) pyrene two quinoline white solid powder (1-DNaANPy), productive rate: 68%; MS (TOF): theoretical value C 52h 34n 4: 714.2783 (M+H) +, experimental value, 714.2799.
Embodiment 3
The preparation of 2-DNaANPy:
The preparation process of its preparation process and DPhANPy is similar, be in d step with the preparation process difference of DPhANPy, the 2-naphthalene boronic acids of usining replaces phenylo boric acid as starting raw material, can make the 7-tertiary butyl-1,3-bis-(2-naphthyl) pyrene two quinoline white solid powder (2-DNaANPy), productive rate: 72%; MS (TOF): theoretical value C 52h 34n 4: 714.2783 (M+H) +, experimental value, 714.2795.
Embodiment 4
The preparation of DPNANPy:
The preparation process of its preparation process and DPhANPy is similar, be in d step with the preparation process difference of DPhANPy, the 1-phenanthryl boric acid of usining replaces phenylo boric acid as starting raw material, can make the 7-tertiary butyl-1,3-bis-(1-phenanthryl) pyrene two quinolines (DPNANPy) white solid powder, productive rate: 68%; MS (TOF): theoretical value C 60h 38n 4: 814.3096 (M+H) +, experimental value, 814.3544.
Embodiment 5
The preparation of DPhCzANPy:
The preparation process of its preparation process and DPhANPy is similar, be in d step with the preparation process difference of DPhANPy, 3-(9-phenyl carbazole) boric acid of usining replaces phenylo boric acid as starting raw material, can make the 7-tertiary butyl-1,3-bis-(3-(9-phenyl carbazole)) pyrene two quinolines (DPhCzANPy) white solid powder, productive rate: 58%, MS (TOF): theoretical value C 68h 44n 6: 944.3627 (M+H) +, experimental value, 944.3688.
Based on above-mentioned two replacement pyrene two oxazoline derivates, the present invention also provides a kind of two to replace the also application of two oxazoline derivates of pyrenes, is about to its luminescent materials as electroluminescent device.
As shown in the figure, described electroluminescent fluorescent luminescent device comprises anode 1, hole injection layer 2, hole transmission layer 3, luminescent layer 4, electron transfer layer 5, electron injecting layer 6, the negative electrode 7 stacking gradually.Wherein luminescent layer 4 is comprised of two replacement pyrenes two quinoline class fluorescence luminescent materials.In preferred embodiment, described anode is ITO, and described negative electrode is aluminium electrode, and described hole injection layer is by MoO 3form, described hole transmission layer is comprised of NPB, and described electron transfer layer is by TPBi(1,3,5-tri-((N-phenyl) benzimidazolyl-) benzene) form, described electron injecting layer is by LiF(lithium fluoride) form.The concrete preferred dimensions of each layer is, the thickness of described hole injection layer is 10 nm, and described hole transmission layer is 40 nm, the thickness of described luminescent layer is 40 nm, the thickness of described electron transfer layer is 40 nm, and the thickness of described electron injecting layer is 1 nm, and the thickness of described aluminium electrode is 150 nm.
In the present invention; two replacement pyrenes of the present invention two oxazoline derivates have hole, electric transmission speed relatively preferably; be connected with blue light fluorophor; can strengthen well the rigidity of whole compound; make the degreeof tortuosity of compound structure become large, can well strengthen compound vitreous conversion temp, strengthen the stability of luminescent device; while is pi-pi accumulation and the excimer of Fluorophotometry luminophor molecule preferably, improves luminous efficiency.
Embodiment 5
Method by vacuum evaporation is prepared into the luminescent layer of electroluminescent device using two replacement pyrenes two oxazoline derivates described in embodiment 1 ~ 4 as blue light fluorescence luminescent material.
The EL device structure of testing in the present embodiment is: ITO/ MoO 3(10 nm)/NPB(40 nm)/luminescent layer (40 nm)/TPBi (40 nm)/LiF (1 nm)/Al.The device architecture that is prepared with OLED with embodiment 1 ~ 4 gained compound is as shown in table 1.
Table 1 is prepared with the device architecture of OLED with embodiment 1 ~ 4 gained compound
Device number Device architecture
Device
1 ITO/MoO 3(10nm)/NPB(40nm)/DPhANPy(40nm)/TPBi(40nm)/ LiF(1nm)/Al
Device 2 ITO/MoO 3(10nm)/NPB(40nm)/1-DNaANPy(40nm)/TPBi(40nm)/ LiF(1nm)/Al
Device 3 ITO/MoO 3(10nm)/NPB(40nm)/2-DNaANPy(40nm)/TPBi(40nm)/ LiF(1nm)/Al
Device 4 ITO/MoO 3(10nm)/NPB(40nm)/DPNANPy(40nm)/TPBi(40nm)/LiF(1nm)/Al
Device
5 ITO/MoO 3(10nm)/NPB(40nm)/DPhCzANPy(40nm)/TPBi(40nm)/ LiF(1nm)/Al
In above-mentioned example, current density-current efficiency curve of device and electroluminescent spectrum are that the Keithley source measuring system (Keithley 2400) by the silicon photoelectric diode with overcorrection records, and all measurements all complete in atmosphere at room temperature.
From Fig. 2 and Fig. 3, can find out, made device 4 and the most frequently used dark blue fluorescence material 1-methyl-9, the luminous efficiency of 10-bis-(2-naphthyl) anthracene (MADN) is compared, luminous efficiency obviously improves, according to experimental data, calculating the present invention utilizes the best photochromic of the prepared electroluminescent device of DPNANPy to reach (0.15,0.18), high-high brightness has reached 34550cd/m simultaneously 2maximum power efficiency reaches 4.9 cd/A, and under high brightness, efficiency roll-off is less, and its trigger voltage is less than 3.1 V simultaneously, be one of current blue light fluorescence radiation device power efficiency high value, device performance is far above take the device that the most frequently used material MADN is luminescent material.
In sum; two replacement pyrenes of the present invention two oxazoline derivates have hole, electric transmission speed relatively preferably; be connected with blue light fluorophor; can strengthen well the rigidity of whole compound; make the degreeof tortuosity of compound structure become large, can well strengthen compound vitreous conversion temp, strengthen the stability of luminescent device; while is pi-pi accumulation and the excimer of Fluorophotometry luminophor molecule preferably, improves luminous efficiency.Therefore, two replacement pyrenes two oxazoline derivates are conducive to the stable of device and make it obtain good electroluminescent properties, be conducive to develop efficient full-color display, can be widely used in the higher OLED large screen display of brightness requirement and OLED white-light illuminating field.
Should be understood that, application of the present invention is not limited to above-mentioned giving an example, and for those of ordinary skills, can be improved according to the above description or convert, and all these improvement and conversion all should belong to the protection domain of claims of the present invention.

Claims (10)

1. two replace pyrene two oxazoline derivates, it is characterized in that, its general structure is as follows:
Figure 2013104775654100001DEST_PATH_IMAGE001
, wherein, Ar is aromatic group.
2. according to claim 1 two replace pyrene two oxazoline derivates, it is characterized in that, Ar is
Figure 833705DEST_PATH_IMAGE002
,
Figure 2013104775654100001DEST_PATH_IMAGE003
, ,
Figure 2013104775654100001DEST_PATH_IMAGE005
or
Figure 389899DEST_PATH_IMAGE006
.
3. as claimed in claim 1 two replace an also preparation method for two oxazoline derivates of pyrene, it is characterized in that, it comprises step:
A, 2-tertiary butyl pyrene is dissolved in to CH 2cl 2in solution, and will contain BTMABr 3cH 2cl 2solution drips in mixed solution, and at room temperature nitrogen protection reaction 3 ~ 8h, after question response completes, adds the shrend reaction of going out, with dichloromethane extraction 3 ~ 5 times, merge organic phase, add anhydrous sodium sulfate drying, filter, the organic solvent of removing wherein obtains the 7-tertiary butyl-1,3-dibromo pyrene;
B, by the 7-tertiary butyl-1,3-dibromo pyrene is dissolved in the mixing solutions of methylene dichloride and Isosorbide-5-Nitrae-dioxy six alkane, stirs 30 min, under nitrogen protection, adds successively NaIO 4, H 2o and RuCl 3, at room temperature stir 15 ~ 20h, the black reaction liquid obtaining is poured in excessive frozen water solution, organic phase layering, uses dichloromethane extraction 3 ~ 5 times, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent evaporate to dryness wherein, its crude product is purified by chromatographic column and is obtained glassy yellow solid 1, the bromo-7-of 3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones;
Under C, nitrogen environment protection, add successively the bromo-7-of 1,3-bis-tertiary butyl-4,5,9,10-, tetra-pyrene quinones, O-Phenylene Diamine, add acetic acid to dissolve simultaneously, reflux 3 ~ 6h, question response liquid is cooled to room temperature, add the shrend reaction of going out, dichloromethane extraction 3 ~ 5 times for gained mixed solution, merges organic phase, add anhydrous magnesium sulfate drying, filter, solvent is wherein evaporated, the crude product obtaining is purified with flash chromatography column chromatography method, obtains the yellow solid 7-tertiary butyl-1,3-dibromo pyrene two quinolines;
D, by the 7-tertiary butyl-1 obtaining, 3-dibromo pyrene two quinolines, the boric acid that comprises aryl are dissolved in toluene solution, add wet chemical and dehydrated alcohol simultaneously, and add catalyst P d (PPh simultaneously 3) 4, in nitrogen environment, be heated to 70 ~ 180 ℃ of lucifuge reactions and reflux 3 ~ 48 hours; Then be cooled to room temperature, add water washing, with dichloromethane extraction, merge organic phase, anhydrous sodium sulfate drying, filters, and removes organic solvent, obtains white solid powder two replace pyrene two oxazoline derivates with column chromatography method.
4. according to claim 3 two replace the also preparation method of two oxazoline derivates of pyrene, it is characterized in that, in described step D, the boric acid that comprises aryl is phenylo boric acid, 1-naphthalene boronic acids, 2-naphthalene boronic acids, 1-phenanthryl boric acid or 3-(9-phenyl carbazole) boric acid.
5. according to claim 3 two replace the also preparation method of two oxazoline derivates of pyrene, it is characterized in that, and in described steps A, 2-tertiary butyl pyrene, BTMABr 3and CH 2cl 2the molar mass of solvent is than 1:(2 ~ 4): (4 ~ 10).
6. according to claim 3 two replace the also preparation method of two oxazoline derivates of pyrene, it is characterized in that, and in described step B, the 7-tertiary butyl-1,3-dibromo pyrene, NaIO 4, H 2o and RuCl 3the molar mass of solvent is than being 1:(8 ~ 12): (8 ~ 10): (0.5 ~ 2.0).
7. according to claim 3 two replace the also preparation method of two oxazoline derivates of pyrene, it is characterized in that, in described step C, the bromo-7-of 1,3-bis-tertiary butyl-4,5, the molar mass of 9,10-, tetra-pyrene quinones, O-Phenylene Diamine and acetic acid solvent is than being 1:(2 ~ 2.2): (8 ~ 10).
8. according to claim 3 two replace the also preparation method of two oxazoline derivates of pyrene, it is characterized in that, and in described step D, the 7-tertiary butyl-1,3-dibromo pyrene two quinolines, the boric acid that comprises aryl, salt of wormwood and catalyst P d (PPh 3) 4molar mass than for 1:(2 ~ 6): (5 ~ 50): (0.02 ~ 0.25).
9. as claimed in claim 1 two replace an also application for two oxazoline derivates of pyrene, it is characterized in that, are applied in electroluminescent device.
10. an electroluminescent device, is characterized in that, the anode that described electroluminescent device stacks gradually, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and negative electrode; Described luminescent layer replaces pyrene by two described in claim 1 or 2 and two oxazoline derivates form.
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