CN103289675A - Fluoro-substituted 9, 9'-spirobifluorene blue-light host material, its preparation method and application - Google Patents
Fluoro-substituted 9, 9'-spirobifluorene blue-light host material, its preparation method and application Download PDFInfo
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Abstract
The invention provides a fluoro-substituted 9, 9'-spirobifluorene blue-light host material, its preparation method and application. Structurally, the fluoro-substituted 9, 9'-spirobifluorene blue-light host material contains a 9, 9'-spirobifluorene central core, the periphery of which is modified by different fluoro-substituted (or trifluoromethyl substituted) phenyl groups. By changing the position and the number of peripheral strong electron withdrawing group fluorine or trifluoromethyl, adjusting the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the material, the charge transmission capability, photophysical properties and thermal properties, and making its emission spectrum and a doped object's absorption spectrum well overlapped, the material can effectively absorb energy and transfer the energy to the object, thus causing luminescence of the object and improving device's performance. With good thermal stability and luminescent properties, the material is easy to synthesize and is convenient to purify, and can be widely used in the fields of organic field effect transistors, organic electroluminescent devices, organic laser and organic photovoltaic solar cells, etc.
Description
Technical field
The invention belongs to the organic photoelectric functional material technical field, relate to a kind of blue light material of main part and application thereof, especially a kind of fluorine replacement 9,9 '-spiral shell two fluorenes blue light material of main parts and its preparation method and application.
Background technology
In recent years, organic electroluminescence device is owing to caused interest widely in the potential application aspect full-color demonstration and the light source in scientific circles and industrial community.In order to realize business-like full-color demonstration, Red Green Blue (RGB) luminescent material has obtained very big development.But, be difficult to realize high-level efficiency and good color purity and long-life blue-light device because the broad-band gap of blue light material inherence makes.Therefore, with respect to green glow and ruddiness device, the poor-performing of blue-light device.Although phosphorescence electroluminescent device (PhOLEDs) has a large amount of research, keep efficient and long-life performance the phosphorescent blue optical device but is difficult to.Therefore, aspect full-color demonstration, blue-light fluorescent material still have vital role (Nature 2006,440,908; Appl.Phys.Lett.2008,92,053311; Appl.Phys.Lett.2008,93,073304; J.Mater.Chem.2011,21,13640.).As everyone knows, the Subjective and Objective doped system can effectively be avoided the effect of slightly going out certainly of fluorescent material, efficient, purity of color and the life-span (J.Appl.Phys.1989,65,3610) of improving device.A fundamental principle is to select suitable material of main part, and it can absorb energy effectively and energy is transferred to object, thereby causes the luminous of object.Particularly the absorption spectrum of the emmission spectrum of main body and object can be overlapping effectively.So far report many blue light material of main parts, mainly comprised anthracene class, diphenylethylene, pyrene class, oligomeric fluorenes class, tetraphenyl-silicon class and oligomeric quinoline material etc.Yet, also need the efficient of blue light material, purity of color and device lifetime further to improve, particularly importantly exploitation has the blue light material of main part of good thermal stability and morphological stability and high-luminous-efficiency.
The spiral shell structure is a kind of based on passing through a shared sp
3A kind of rigid structure that the hydridization carbon atom is connected to form two Pi-conjugated systems with identical or different function, it has good amorphous property.Fluorescence luminescent material with spiral shell structure can suppress the formation of excimer effectively, makes that the luminosity of material is unaffected (Chem.Rev.2007,107,1011).Especially, spiral shell two compound of fluorene class have excellent thermostability and chemical stability, high fluorescence quantum efficiency and nondispersive bipolarity carrier transport character (J.Am.Chem.Soc.2003,125,3710; Chem.Commun.2007,1831.).In addition, the highest occupied molecular orbital (HOMO) that fluorination can be by reducing material and lowest unoccupied molecular orbital (LUMO) energy level and stability and the electron-transporting of strongthener make it have character (J.Phys.Chem.Lett.2011,2,648 that bipolarity is transmitted; J.Phys.Chem.C2012, dx.doi.org/10.1021/jp3028929).In addition, the C – H in the fluoro material ... F interaction (similar with hydrogen bond) has important effect when solid-state accumulation, can cause typical π-packing arrangement mode, thereby strengthens charge mobility (Chem.Mater.2011,23,446; Chem.Commun.2007,1003; Chem.Soc.Rev.2011,40,3496.).
Summary of the invention
The object of the present invention is to provide a kind of fluorine to replace 9,9 '-spiral shell two fluorenes blue light material of main parts and its preparation method and application, it is with 9,9 '-the fluorene structured advantage of spiral shell two and the advantage novel fluoro 9 of a class that synthesized designed in conjunction of fluorination, 9 '-spiral shell two fluorenes blue light material of main parts, be that the blue-light device of the non-doping made of luminescent layer has good performance with this material.
The objective of the invention is to solve by the following technical programs:
This fluorine replaces 9,9 '-spiral shell two fluorenes blue light material of main parts be contain 9,9 '-spiral shell two fluorenes centronucleuses, the structure that the peripheral phenyl that replaces with fluorine is modified, it has following molecular structural formula:
In the above-mentioned molecular formula, R
1-R
5Be respectively in hydrogen, fluorine and the trifluoromethyl any one.
Further, more than peripheral strong electron-withdrawing group group's fluorine or trifluoromethyl the position the neighbour of phenyl ring, and contraposition replace, substituent number is 1,2,3,4 or 5.
The present invention also proposes a kind of above-mentioned fluorine and replaces 9,9 '-preparation method of spiral shell two fluorenes blue light material of main parts: by 9 of Ferric Chloride 1 equivalent, the bromine of 9'-spiral shell two fluorenes and 4.3 equivalents at room temperature bromo obtains the reaction intermediate 2 of 1 equivalent, 2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes, and then under tetrakis triphenylphosphine palladium catalysis, carry out the Suzuki linked reaction with phenylo boric acid that the fluorine of 4.3 equivalents or trifluoromethyl replace and obtain target product.
Further, above-mentioned reaction intermediate 2,2 ', 7,7 '-tetrabromo-9,9 '-the synthesizing of spiral shell two fluorenes: to 9 of 1 equivalent, 9 '-chloroform soln of spiral shell two fluorenes and Anhydrous Ferric Chloride in, under 0 ° of C, slowly drip the chloroform soln of the bromine of 4.3 equivalents, the some plate is followed the tracks of reaction 24h; Reaction finishes, and removes remaining bromine with saturated sodium thiosulfate solution and washed reaction liquid respectively, and the anhydrous sodium sulfate drying organic phase is revolved the steaming desolventizing and got crude product, use trichloromethane and ethyl alcohol recrystallization again, obtain the reaction intermediate 2,2 of 1 equivalent ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes.
Described Suzuki linked reaction step is: under the nitrogen atmosphere, in the presence of the catalyzer tetrakis triphenylphosphine palladium of 0.2 equivalent, 2,2 of 1 equivalent ', 7,7 '-tetrabromo-9,9 '-the Suzuki linked reaction takes place with the phenyl-boron dihydroxide of the multiple fluoro of 4.3 equivalents respectively in spiral shell two fluorenes (Spiro-4Br), obtain 1 equivalent to contain 9,9 '-spiral shell two fluorenes centronucleuses, peripheral fluoro fluoro 9,9 with different fluoro phenyl modification structures '-spiral shell two fluorenes class materials.
The present invention also proposes a kind of above-mentioned fluorine and replaces 9,9 '-spiral shell two application of fluorenes blue light material of main part in organic field effect tube, organic electroluminescence device, organic laser and organic photovoltaic solar cell.
The present invention has following beneficial effect:
1) fluoro among the present invention 9,9 '-Heat stability is good of spiral shell two fluorenes blue light material of main parts, the second-order transition temperature height easily forms good amorphous thin film by optimizing the material that forms; Have suitable highest occupied molecular orbital and lowest unoccupied molecular orbital energy level simultaneously, fluorescence and narrower spectrum halfwidth (FWHM) are preferably arranged, the fluorescence quantum efficiency height in solution and solid film.
2) fluoro 9 of the present invention, 9 '-spiral shell two fluorenes blue light material of main parts are by changing position and the number of peripheral strong electron-withdrawing group group's fluorine or trifluoromethyl, can have suitable highest occupied molecular orbital and lowest unoccupied molecular orbital energy level, and the absorption spectrum that makes its emmission spectrum and object BCzVBi has well overlapping, thereby can absorb energy effectively and energy is transferred to object, thereby cause the luminous of object, the performance of boost device.
3) utilize fluoro 9,9 of the present invention '-the blue light emitting device of the non-doping of spiral shell two fluorenes blue light material of main parts preparations, obtained the chromaticity coordinates (CIE of good spectrum
Xy), its corresponding glow peak has good luminous efficiency and luminosity simultaneously near 404nm.
4) utilize fluoro 9,9 of the present invention '-the mix blue light emitting device of preparation of spiral shell two fluorenes blue light material of main parts and BCzVBi, it is luminous to access ethereal blue light, and has low open bright voltage, high brightness, high current efficiency, energy-efficient and high external quantum efficiency.
Description of drawings
Fig. 1 be fluorine provided by the invention replace 9,9 '-structural representation of spiral shell two fluorene materials;
Fig. 2 is the prepared non-doping device ITO/MoO of material 1
3(1nm)/current density-voltage-brightness curve of TcTa (40nm)/1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm);
Fig. 3 is the prepared non-doping device ITO/MoO of material 1
3(1nm)/current efficiency-current density-energy efficiency curve of TcTa (40nm)/1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm);
Fig. 4 be the absorption spectrum of BCzVBi and fluoro 9,9 '-spiral shell two fluorene materials 1,2,3,5,13,18 and 26 emmission spectrum;
Fig. 5 is the prepared doping device ITO/MoO of material 2
3(1nm)/current density-voltage-brightness curve of TcTa (40nm)/2:10vol%BCzVBi (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm);
Fig. 6 is the prepared doping device ITO/MoO of material 2
3(1nm)/current efficiency-current density-energy efficiency curve of TcTa (40nm)/2:10vol% BCzVBi (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm).
Embodiment
This kind fluorine that the present invention proposes replaces 9,9 '-spiral shell two fluorene material blue light material of main parts contain 9,9 '-spiral shell two fluorenes centronucleuses, the structure of peripheral phenyl modification with different fluoro, such material has following molecular structural formula:
In the above-mentioned molecular formula, R
1-R
5Can be hydrogen, fluorine or trifluoromethyl.Peripheral strong electron-withdrawing group group's fluorine or the position of trifluoromethyl can the neighbour of phenyl ring, and contraposition replace, substituent number can be 1,2,3,4 or 5.Such material can be in organic field effect tube, organic electroluminescence device, organic laser and organic photovoltaic solar cell application.
Fluorine of the present invention replaces 9,9 '-preparation method of spiral shell two fluorenes blue light material of main parts is: by 9 of Ferric Chloride 1 equivalent, the bromine of 9'-spiral shell two fluorenes and 4.3 equivalents at room temperature bromo obtains the reaction intermediate 2 of 1 equivalent, 2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes, and then under tetrakis triphenylphosphine palladium catalysis, carry out the Suzuki linked reaction with phenylo boric acid that the fluorine of 4.3 equivalents or trifluoromethyl replace and obtain target product.
Suzuki linked reaction step is: under the nitrogen atmosphere, in the presence of the catalyzer tetrakis triphenylphosphine palladium of 0.2 equivalent, 2,2 of 1 equivalent ', 7,7 '-tetrabromo-9,9 '-the Suzuki linked reaction takes place with the phenyl-boron dihydroxide of the multiple fluoro of 4.3 equivalents respectively in spiral shell two fluorenes (Spiro-4Br), obtain 1 equivalent to contain 9,9 '-spiral shell two fluorenes centronucleuses, peripheral fluoro fluoro 9,9 with different fluoro phenyl modification structures '-spiral shell two fluorenes class materials.
Below in conjunction with drawings and Examples the present invention is done and to describe in further detail:
Referring to Fig. 1, fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts are by 9 of Ferric Chloride, 9'-spiral shell two fluorenes and bromine at room temperature bromo obtain reaction intermediate 2,2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (2,2 ', 7,7 '-tetrabromo-9,9 '-spirobifluorene, Spiro-4Br), and then under tetrakis triphenylphosphine palladium catalysis, carry out the Suzuki linked reaction with phenylo boric acid that fluorine or trifluoromethyl replace and obtain target product.
Wherein intermediate product 2,2 ', 7,7 '-tetrabromo-9,9 '-the synthesizing of spiral shell two fluorenes: to 9,9 '-spiral shell two fluorenes (6.52g, 20.6mmol) and Anhydrous Ferric Chloride (FeCl
3, in the chloroform soln of 60mL 10mg), under 0 ° of C, slowly drip 10mL and contain bromine (4.45mL, chloroform soln 86.6mmol) (dripping more than the 1h), some plate tracking reaction (reaction 24h).Reaction finishes, and removes remaining bromine with saturated sodium thiosulfate solution and washed reaction liquid respectively, the anhydrous sodium sulfate drying organic phase, steam desolventize crude product, with trichloromethane and ethyl alcohol recrystallization, obtain white solid 11.3g, productive rate 87%.
Suzuki linked reaction step is: under the nitrogen atmosphere, in the presence of the catalyzer tetrakis triphenylphosphine palladium, 2,2 ', 7,7 '-tetrabromo-9,9 '-the Suzuki linked reaction takes place with the phenyl-boron dihydroxide of multiple fluoro respectively in spiral shell two fluorenes (Spiro-4Br), obtain containing 9,9 '-spiral shell two fluorenes centronucleuses, peripheral fluoro fluoro 9,9 with different fluoro phenyl modification structures '-spiral shell two fluorenes class materials.
Embodiment 2: fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts 1 synthetic:
Under nitrogen atmosphere, to 30mL THF and 10mL, 2.0molL
-1K
2CO
3In the solution, add 2,2 successively ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (1.1g, 1.74mmol), the 2-fluorobenzoic boric acid (1.40g, 10mmol) and Pd (PPh3) 4(0.40g, 0.35mmol).Reaction back mixture heating up backflow 24h, some plate following response.Reaction finishes, and cooling adds the water stopped reaction.Product CH
2Cl
2Extract salt washing organic phase, anhydrous MgSO
4Drying is revolved inspissation contracting desolventizing, gets 1.05g white solid 1 with ethyl acetate and sherwood oil column chromatography.
1H?NMR(CDCl
3,400MHz):δ6.98(s,4H),7.01-7.10(m,8H),7.18-7.23(m,4H),7.28-7.31(t,J=7.6Hz,4H),7.62(d,J=7.6Hz,4H),7.93(d,J=8.0Hz,4H)。
Embodiment 3: fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts 5 synthetic:
Under nitrogen atmosphere, to 30mL THF and 10mL, 2.0molL
– 1K
2CO
3In the solution, add 2,2 successively ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (1.1g, 1.74mmol), 2,4 two-fluorobenzoic boric acids (1.58g, 10mmol) and Pd (PPh
3)
4(0.40g, 0.35mmol).Reaction back mixture heating up backflow 24h, some plate following response.Reaction finishes, and cooling adds the water stopped reaction.Product CH
2Cl
2Extract salt washing organic phase, anhydrous MgSO
4Drying is revolved inspissation contracting desolventizing, gets 1.18g white solid 5 with ethyl acetate and sherwood oil column chromatography.
1H?NMR(CDCl
3,400MHz):δ6.78-6.85(m,8H),7.91(s,4H),7.23-7.25(m,4H),7.57(d,J=8.0Hz,4H),7.93(d,J=8.0Hz,4H)。
Embodiment 4: fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts 13 synthetic:
Under nitrogen atmosphere, to 30mL THF and 10mL, 2.0molL
-1K
2CO
3In the solution, add 2,2 successively ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (1.1g, 1.74mmol), 2,4 two-fluorobenzoic boric acids (2.00g, 11.36mmol) and Pd (PPh
3)
4(0.40g, 0.35mmol).Reaction back mixture heating up backflow 24h, some plate following response.Reaction finishes, and cooling adds the water stopped reaction.Product CH
2Cl
2Extract salt washing organic phase, anhydrous MgSO
4Drying is revolved inspissation contracting desolventizing, gets 1.40g white solid 13 with ethyl acetate and sherwood oil column chromatography.
1H?NMR(CDCl
3,400MHz):δ6.86(s,4H),7.03-7.06(t,J=7.6Hz,8H),7.60(d,J=8.0Hz,4H),8.00(d,J=8.0Hz,4H)。
Embodiment 5: fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts 18 synthetic:
Under nitrogen atmosphere, to 30mL THF and 10mL, 2.0molL
– 1K
2CO
3In the solution, add 2,2 successively ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (1.1g, 1.74mmol), 2,4 two-fluorobenzoic boric acids (1.90g, 10mmol) and Pd (PPh
3)
4(0.40g, 0.35mmol).Reaction back mixture heating up backflow 24h, some plate following response.Reaction finishes, and cooling adds the water stopped reaction.Product CH
2Cl
2Extract salt washing organic phase, anhydrous MgSO
4Drying is revolved inspissation contracting desolventizing, gets 1.10g white solid 18 with ethyl acetate and sherwood oil column chromatography.
1H?NMR(CDCl
3,400MHz):δ6.98(s,4H),7.02-7.10(m,8H),7.21(d,J=7.2Hz,4H),7.28-7.30(t,J=8.0Hz,4H),7.63(d,J=8.0Hz,4H),7.93(d,J=8.0Hz,4H)。
Embodiment 6: fluoro 9,9 '-spiral shell two fluorenes blue light material of main parts 26 synthetic:
Under nitrogen atmosphere, to 30mL THF and 10mL, 2.0molL
-1K
2CO
3In the solution, add 2,2 successively ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes (1.1g, 1.74mmol), 2,4 two-fluorobenzoic boric acids (2.58g, 10mmol) and Pd (PPh
3)
4(0.40g, 0.35mmol).Reaction back mixture heating up backflow 24h, some plate following response.Reaction finishes, and cooling adds the water stopped reaction.Product CH
2Cl
2Extract salt washing organic phase, anhydrous MgSO
4Drying is revolved inspissation contracting desolventizing, gets 1.70g white solid 26 with ethyl acetate and sherwood oil column chromatography.
1H?NMR(CDCl
3,400MHz):δ6.99(s,4H),7.75-7.78(m,8H),7.88(s,8H),8.13(d,J=8.0Hz,4H)。
Embodiment 7: adopt compound 1 luminescent material, MoO
3As hole-injecting material, TcTa is as hole mobile material, and TPBi is as electron transport material, LiF is as the electronics injecting material, and the electroluminescent device structure that has prepared is as follows:
Glass substrate/ITO/MoO
3(1nm)/TcTa (40nm)/1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm).
(1) is carved with the cleaning of the glass substrate of ITO in advance: utilize the ultrasonic and ultrasonic method of deionized water of the washing composition of heat that the transparent conduction base sheet ito glass is cleaned, place it in after the cleaning under the infrared lamp and dry, wherein the ITO film above the conductive substrate is as the anode layer of device, the square resistance of ITO film is 5 Ω～100 Ω, and thickness is 80～280nm.
(2) preparation of each organic function layer: the substrate of doing after the drying treatment is put in the vacuum chamber, evaporation hole mobile material successively, the evaporation speed of material film is 0.01～0.5nm/s, thickness is 40nm; At hole mobile material evaporation luminescent layer, the evaporation speed of material film is 0.01～0.5nm/s, and thickness is 20nm; Evaporation electron transport material on luminescent layer, the evaporation speed of material film is 0.01～0.5nm/s, thickness is 40nm.
(3) preparation of negative electrode: keep above-mentioned vacuum chamber internal pressure constant, the Al composite cathode layer of the LiF of evaporation 1nm and 100nm successively on above-mentioned electron transfer layer.
(4) ready-made device is taken out vacuum chamber, the current-voltage-brightness of test component-efficiency characteristic and electroluminescent spectrum under atmospheric environment.
Fig. 2 is the prepared non-doping device ITO/MoO of the prepared device material of material 11
3(1nm)/and current density-voltage-brightness curve figure of TcTa (40nm)/1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm), opening bright voltage is 4.8V, maximum luminousing brightness can reach 917cd m
-1Fig. 3 is the prepared non-doping device ITO/MoO of material 1
3(1nm)/and current efficiency-current density-energy efficiency diagram of TcTa (40nm)/1 (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm), its maximum current efficient is 0.53cd A
– 1, for energy efficiency be 0.29lm W
-1, its maximum glow peak is 404nm.Because it is luminous to have obtained royal purple light, so high relatively device efficiency is because due to the high fluorescence quantum efficiency of fluoro spiral shell two fluorenes class materials itself.Obtain lower bright voltage and the high electroluminescent efficiency of opening and show that also hole and electronics very effectively are injected into the fluoro spiral shell two fluorenes class luminescent materials of broad-band gap.
Fig. 4 is absorption spectrum and the fluoro 9 of BCzVBi, 9 '-spiral shell two fluorene materials 1,2,3,5,13,18 and 26 emmission spectrum, as seen as the fluoro 9 of main body, 9 '-absorption spectrum that the emmission spectrum of spiral shell two fluorene materials and BCzVBi mix has well overlappingly, shows between main body and the doping to have efficiently
Energy shifts.
Fig. 5 is the prepared doping device ITO/MoO of material 2
3(1nm)/and current density-voltage-brightness curve figure of TcTa (40nm)/2:10vol%BCzVBi (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm), opening bright voltage is 3.4V, maximum luminousing brightness is 10820cdm
-1Fig. 6 is the prepared doping device ITO/MoO of material 2
3(1nm)/and current efficiency-current density-energy efficiency graphic representation of TcTa (40nm)/2:10vol%BCzVBi (20nm)/TPBi (40nm)/LiF (1nm)/Al (100nm), the maximum current efficient of device is 10.52cdA
– 1, corresponding energy efficiency is 8.53lm W
-1, maximum external quantum efficiency is 6.63%.The high electroluminescent efficiency of BCzVBi doping device mainly be because fluoro 9,9 '-spiral shell two fluorenes material of main parts with mix between energy transfer efficiently.In addition, hole trap and electronics are in the direct compound electroluminescent efficiency that also helps to improve of dopant material.This high-level efficiency is much better than the BCzVBi doping device of bibliographical information.
Claims (6)
- A fluorine replace 9,9 '-spiral shell two fluorenes blue light material of main parts, it is characterized in that: this material be contain 9,9 '-spiral shell two fluorenes centronucleuses, the structure that the peripheral phenyl that replaces with fluorine is modified, it has following molecular structural formula:
In the above-mentioned molecular formula, R 1-R 5Be respectively in hydrogen, fluorine and the trifluoromethyl any one. - Fluorine according to claim 1 replace 9,9 '-spiral shell two fluorenes blue light material of main parts, it is characterized in that: peripheral strong electron-withdrawing group group's fluorine or the position of trifluoromethyl the neighbour of phenyl ring, and contraposition replace, substituent number is 1,2,3,4 or 5.
- 3. the described fluorine of claim 1 replaces 9,9 '-preparation method of spiral shell two fluorenes blue light material of main parts, it is characterized in that: by 9 of Ferric Chloride 1 equivalent, the bromine of 9'-spiral shell two fluorenes and 4.3 equivalents at room temperature bromo obtains the reaction intermediate 2 of 1 equivalent, 2 ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes, and then under tetrakis triphenylphosphine palladium catalysis, carry out the Suzuki linked reaction with phenylo boric acid that the fluorine of 4.3 equivalents or trifluoromethyl replace and obtain target product.
- 4. preparation method according to claim 3, it is characterized in that, reaction intermediate 2,2 ', 7,7 '-tetrabromo-9,9 '-the synthesizing of spiral shell two fluorenes: to 9 of 1 equivalent, 9 '-chloroform soln of spiral shell two fluorenes and Anhydrous Ferric Chloride in, under 0 ° of C, slowly drip the chloroform soln of the bromine of 4.3 equivalents, the some plate is followed the tracks of reaction 24h; Reaction finishes, and removes remaining bromine with saturated sodium thiosulfate solution and washed reaction liquid respectively, and the anhydrous sodium sulfate drying organic phase is revolved the steaming desolventizing and got crude product, use trichloromethane and ethyl alcohol recrystallization again, obtain the reaction intermediate 2,2 of 1 equivalent ', 7,7 '-tetrabromo-9,9 '-spiral shell two fluorenes.
- 5. preparation method according to claim 3, it is characterized in that, Suzuki linked reaction step is: under the nitrogen atmosphere, in the presence of the catalyzer tetrakis triphenylphosphine palladium of 0.2 equivalent, 2 of 1 equivalent, 2 ', 7,7 '-tetrabromo-9,9 '-the Suzuki linked reaction takes place with the phenyl-boron dihydroxide of the multiple fluoro of 4.3 equivalents respectively in spiral shell two fluorenes (Spiro-4Br), obtain 1 equivalent to contain 9,9 '-spiral shell two fluorenes centronucleuses, peripheral fluoro fluoro 9,9 with different fluoro phenyl modification structures '-spiral shell two fluorenes class materials.
- A fluorine as claimed in claim 1 replace 9,9 '-spiral shell two application of fluorenes blue light material of main part in organic field effect tube, organic electroluminescence device, organic laser and organic photovoltaic solar cell.
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| CN103666453A (en) * | 2013-11-22 | 2014-03-26 | 宁波大学 | Blue fluorescent material containing trifluoromethylfluorene and preparation method thereof |
| CN103666453B (en) * | 2013-11-22 | 2014-11-19 | 宁波大学 | Blue fluorescent material containing trifluoromethylfluorene and preparation method thereof |
| CN104844464A (en) * | 2015-03-13 | 2015-08-19 | 中节能万润股份有限公司 | Deprotection 9,9'-spirobifluorene dendritic compound and preparation method and application |
| CN104844464B (en) * | 2015-03-13 | 2016-08-24 | 中节能万润股份有限公司 | A kind of 9,9 '-Spirobifluorene dendrimer and preparation method and application |
| CN105198792A (en) * | 2015-09-14 | 2015-12-30 | 中节能万润股份有限公司 | Carbazole diarylamine dendritic compound as well as preparation method and application of carbazole diarylamine dendritic compound |
| CN105198792B (en) * | 2015-09-14 | 2018-03-23 | 中节能万润股份有限公司 | A kind of carbazole diaryl-amine class dendrimer and its preparation method and application |
| CN113087593A (en) * | 2021-04-08 | 2021-07-09 | 南京工业职业技术大学 | Trifluoromethyl benzene functionalization-based spirofluorene organic laser material, and microcrystal preparation and application |
| CN114163379A (en) * | 2021-04-19 | 2022-03-11 | 闽都创新实验室 | Fluorocarbazolyl diphenylethylene biphenyl compound and preparation method and application thereof |
| CN114957092A (en) * | 2022-05-05 | 2022-08-30 | 南京邮电大学 | Organic luminescent material, preparation method and application |
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