CN102977006A - Pyridine-fluorene organic electrophosphorescence main body luminescent material and preparation method thereof - Google Patents
Pyridine-fluorene organic electrophosphorescence main body luminescent material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a pyridine-fluorene organic electrophosphorescence main body luminescent material and a preparation method thereof, relating to new-generation organic luminescent display materials and technology. Due to the rigid structure, the luminescent material has high triplet energy level and favorable hole injection and transmission performance; and due to the three-dimensional large-volume steric hindrance effect, the luminescent material has stable amorphous state, and thus, can be widely used in organic light-emitting diodes. The specific design structure of the pyridine-fluorene main body material is disclosed in the specification. The invention particularly relates to a preparation method and application in organic light-emitting diode devices. The material has the advantages of high luminescence efficiency, high heat stability, high glass transition temperature and simple synthesis method, and can effectively inhibit concentration quenching and dimer luminescence. The preliminary structure as the main body material implements red-green-blue tricolor organic electroluminescent devices. The compounds have wide application prospects and huge commercial value in the aspects of electrophosphorescent main body materials.
Description
Technical field
The present invention is specifically related to make the preparation method of its functionalization based on 9 hydroxyls with 9-hydroxyl-9-(2-pyridyl) fluorenes with the aromatic ring replacement, and relates to step and raw material that these materials adopt in preparation process.
Background technology
Since Deng Qingyun in 1987 had reported that the high brightness low voltage has the Organic Light Emitting Diode of sandwich structure, organic electroluminescent LED was as flat pannel display of future generation and solid state lighting technology and be subject to numerous scientific workers' great attention and greatly research enthusiasm of industry member elite.Indicating meter with inorganic materials is compared, organic elctroluminescent device has its many advantages that can't reach, as: material source is wide, energy consumption is little, lightweight, volume is little, manufacturing process is simple, contrast gradient is high, the visual angle is wide, driving voltage is low, color is adjustable, fast response time, luminous efficiency high, flexible show etc.Therefore, being described as " 21 century flat panel display ", is the technique of display of generally acknowledge the most desirable of industry and tool development prospect.。
Electroluminescent organic material is divided into fluorescence and phosphorescence two class materials.And organic electroluminescent fluorescent materials makes its device internal quantum efficiency have 25% theoretical limit because its triplet excitons exists spin to prohibit and can not effectively utilize its triplet excitons energy always.In contrast, the organic molecule electromechanical phosphorescent material since because of the Spin-orbit coupling interaction of heavy metal so that its triplet excitons is effectively luminous by passing through between being, thereby so that the organic molecule phosphor material break through the one theory of internal quantum efficiency 25% and reach 100%.The performance such as in addition, its simple preparation method and color be adjustable also enjoys scientific worker's favor.Baldo in 2001 etc. are (ppy)
2Ir (acac) is entrained among the TAZ, has prepared the high efficiency phosphorescent device, and the internal quantum efficiency of this device almost reaches 100 %, and its external quantum efficiency reaches 19%.So that the efficient of electroluminescent device obtains unprecedented raising and has caused great sensation.Yet organic electro phosphorescent device normally is doped to guest materials in the material of main part, to prevent that guest materials under solid state concentration quenching occuring or triplet state is buried in oblivion.Therefore preparing effective material of main part is the key of preparation stability and high efficiency phosphorescence device.In order to obtain efficient phosphorescence device, desirable material of main part need to satisfy following condition: at first, material of main part need to have suitable triplet (triplet that is material of main part is greater than guest materials), to prevent the energy counter-rotating; Secondly, suitable HOMO and lumo energy can be complementary with the energy level of adjacent carrier blocking layers, reduce driving voltage and improve luminous efficiency; Again, material of main part will have high thermostability and good film forming characteristics, to improve the stability of device; At last, material of main part need to have good carrier injection and transmittability and effectively equilbrium carrier make its effective recombination luminescence in guest materials, to improve the luminous efficiency of device.Therefore, the synthetic effective material of main part of design is the key of preparation stability and high efficiency luminescent device.
Pyridine fluorenes class has stable amorphous state and high thermostability because having larger three-dimensional space steric effect, can concentration quenching and the triplet state of establishment object phosphor material under filminess bury in oblivion.In addition, fluorenes has higher triplet (2.95 eV), can make it both have good photoelectric properties by its 9-position is modified and have suitable triplet because of non-conjugated connection.Based on this thought, the present invention passes through friedel-crafts reaction with 9-hydroxyl-9 (2-pyridyl) fluorenes, succinctly prepared efficiently a series of luminescent materials with 9-hydroxyl-9 (2-pyridyl) fluorenes functionalization, and to having carried out preliminary study in the application aspect the OLEDs.
In a word, the present invention is under the prerequisite to current electroluminescent organic material overall understanding, and tracking organic electronic devices forward position is dynamic, launches around preparation and the dependent interaction mechanism thereof synthetic, El element of electroluminescent organic material.Take molecular designing as guidance, the effective material of main part of design synthesizing stable, the phosphorescence device of preparation stability and high efficiency.
Summary of the invention
Technical problem:Purpose of the present invention provides a kind of pyridine fluorenes class luminescent material and its preparation method and application, and design is synthetic based on a kind of pyridine fluorenes class luminescent material, and effective material of main part is stablized in preparation, and there is widespread use in it aspect electroluminescent, the memory device.
Technical scheme:The present invention is a kind of pyridine fluorenes class luminescent material and its preparation method and application, and this material is 9 hydrogen atom positions of fluorenes in the pyridine fluorenes class to be replaced with different aromatic rings make its functionalization, and it has following structure:
General formula
I
General formula
IIn, n=1 or 2, Ar are aromatic ring structure, its array structure specific as follows:
。
General formula
IThe compound of representative all contains pyridine fluorenes class, and the functional functional group A r of all introducings all is connected to 9 of fluorenes.
The preparation method of pyridine fluorenes organic electrofluorescent main body luminescent material of the present invention is:
A. get the 2-bromopyridine and join single necked round bottom flask, low temperature stirs under dry ice acetone and nitrogen protection, getting n-Butyl Lithium slowly adds in the reactor, low-temp reaction 0.5-5 hour, get Fluorenone and inject constant pressure funnel with the THF dissolving, and add the ether dilution, be added drop-wise in the reactor, low-temp reaction 1-5 hour, normal-temperature reaction then; Use water treatment, transfer pH to be about neutrality with acetic acid, use dichloromethane extraction, the organic phase anhydrous magnesium sulfate drying, concentrated, column chromatography gets product;
B. get in 9-hydroxyl-9-(2-pyridyl) fluorenes, 2-thiotolene, the acetic acid heated and stirred dissolving adding reactor, then add the vitriol oil, be heated to back flow reaction 10-48 hour, question response is cooled to room temperature, adding cold water stirs, then add aqueous sodium hydroxide solution to solution and be alkalescence, with dichloromethane extraction repeatedly, merge the organic phase anhydrous magnesium sulfate drying; After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating; Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product.
Spiro-iridium organic electrophosphorescenmaterial material of the present invention is used for organic electroluminescent diode apparatus, wherein the structure of LED device is transparent anode/luminescent layer/electron injecting layer/negative electrode, wherein, luminescent layer is the Subjective and Objective system, and spiral shell fluorenes xanthene title complex is as the guest materials of luminescent layer.
Device architecture is as follows: suitable guest materials is doped to preparation red, green, blue three primary colours organic electroluminescence device in the synthetic pyridine fluorenes class of design.
But the present invention has 3-D solid structure establishment concentration quenching in conjunction with the pyridine fluorenes, introduces different functional luminous energy group's timely adjustment spectrum and energy level thereof for 9 that are combined in simultaneously fluorenes, thereby reaches synthetic succinct efficiently material of main part.
Beneficial effect:Characterized the complex whorl aryl fluorene material structure by ultimate analysis, infrared spectra (FTIR), nucleus magnetic resonance (NMR), chromaticness online (GCMS), gel chromatography (GPC), by the thermostability that thermogravimetric analysis and differential thermal analysis have been tested material, characterized their light, electrochemical properties by Ultraluminescence spectrum and cyclic voltammetric method.This class material shows good thermostability in thermogravimetric analysis and differential thermal analysis, ultraviolet, fluorescence and electrochemical analysis show that it has good photoelectric properties.Therefore, this class material can be widely used in Organic Light Emitting Diode, organic laser, Organic Electricity memory device, organic field-effect tube etc.
On this basis, design preliminary electroluminescent device and estimated pyridine fluorenes luminescent properties.Wherein the structure of device is transparent anode/luminescent layer/electron injecting layer/negative electrode, wherein the pyridine fluorenes by the vacuum evaporation mode prepare, negative electrode prepares by vacuum coating technology.Experimental result shows: these pyridine fluorenes have shown efficient phosphorescent emissions performance, with FIrpic, Ir (ppy)
3, Ir (MDQ)
2(acac) etc. guest materials is by steamings degree technology realization red, green, blue three-color light-emitting technology.
Major advantage of the present invention is:
1. simple, the mild condition of synthesis step;
2. high thermal stability and second-order transition temperature have been kept.
3. has suitable triplet
4. have suitable HOMO and lumo energy
5. has large space steric effect
Description of drawings
Fig. 1. 9-(2-pyridyl)-9-(2-thienyl) fluorenes
1HNMR figure;
Fig. 2. 9-(2-pyridyl)-9-(2-thiotolene base) fluorenes
1HNMR figure;
Fig. 3. 9-(2-pyridyl)-9-(2-(2,2-bithienyl)) fluorenes
1HNMR figure;
Fig. 4. 2,2-two (9-(2-pyridine)-fluorenyl)-2,2 ', 2 ' '-three thiophene
1HNMR figure;
Fig. 5. 9-(2-chloroethyl)-3,6-two (9-(2-pyridine)-fluorenyl) carbazole
1HNMR figure;
Fig. 6. 3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole and
1HNMR figure;
Fig. 7. 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole
1HNMR figure;
Fig. 8. with 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole electroluminescent spectrogram.
Fig. 9. 3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole electroluminescent spectrogram.
Figure 10 2, and 2-two (9-(2-pyridine)-fluorenyl)-2,2 ', 2 ' '-three thiophene is respectively the main body material of device
Material electroluminescent spectrogram.
The brightness of Figure 11 blue-light device B1-B4-voltage-to-current densimetric curve.
The external quantum efficiency of Figure 12 blue-light device B1-B4-current density curve.
Figure 13 is the structural representation of luminescent device.
Embodiment
Further describe technical scheme of the present invention below in conjunction with embodiment, but these embodiment and unrestricted embodiments of the present invention.The present invention has multiple different embodiment, has more than to be limited to content described in this specification sheets.Those skilled in the art is in the situation of the present application spirit, and the scheme of finishing should be within the scope of the invention.
Embodiment 1:9-(2-pyridyl)-9-(2-thienyl) fluorenes
Get successively 9-hydroxyl-9 (2-pyridyl) fluorenes (0.5180 g, 2 mmol), thiophene (1.28 mL, 16 mmol), the dissolving of acetic acid 200 mL heated and stirred, then add the vitriol oil 4 mL and be heated to 120 ℃ of 24 h that reflux.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate: 40%).GC-MS?(EI)?m/z?325?[M
+];1H?NMR?(400?MHz,?CDCl
3):?δ?(ppm)?8.66?(s,?1H),?7.78?(D,?
J?=?7.52,?2H),?7.69?(D,?
J?=?7.57,?2H),?7.46?(m,?1H),?7.40?(t,?
J?=?6.54,?2H),?7.31?(t,?
J?=?6.57,?2H),?7.13?(m,?2H),?7.05?(D,?
J?=?7.96,?1H),?6.86?(t,?
J?=?3.66,?1H),?6.77?(D,?
J?=?4.62,?1H)。
Synthesizing of embodiment 2:9-(2-pyridyl)-9-(2-thiotolene base) fluorenes:
Get successively 9-hydroxyl-9 (2-pyridyl) fluorenes (0.5180 g, 2 mmol), 2-thiotolene (1.57 mL, 16 mmol), the dissolving of acetic acid 200 mL heated and stirred, then add the vitriol oil 4 mL and be heated to 120 ℃ of backflow 24h.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate: 42%).GC-MS?(EI)?m/z?325?[M
+];1H?NMR?(400?MHz,?CDCl
3):?δ?(ppm)?8.70?(s,?1H),?7.77?(D,?
J?=?7.55,?2H),?7.68?(D,?
J?=?7.53,?2H),?7.50?(m,?1H),?7.39?(t,?
J?=?7.28,?2H),?7.31?(t,?
J?=?7.44,?2H),?7.11?(t,?
J?=?4.83,?1H),?7.05?(D,?
J?=?7.99,?1H),?6.52?(m,?2H),?2.38?(s,?3H)。
Synthesizing of embodiment 3:9-(2-pyridyl)-9-(2-(2,2-bithienyl)) fluorenes:
Get successively 9-hydroxyl-9 (2-pyridyl) fluorenes (0.5180 g, 2 mmol), 2, then 2-two bithiophenes (0.1663 g, 1 mmol), the dissolving of acetic acid 200 mL heated and stirred add the vitriol oil 4 mL and are heated to 120 ℃ of backflow 24h.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate: 30%).GC-MS?(EI)?m/z?325?[M
+];1H?NMR?(400?MHz,?CDCl
3):?δ?(ppm)?8.70?(s,?1H),?7.80?(d,?
J?=?7.35,?2H),?7.73?(d,?
J?=?7.57,?2H),?7.45?(m,?3H),?7.40?(t,?
J?=?7.43,?2H),?7.15?(m,?2H),?7.0613?(m,?2H),?6.93?(m,?2H),?6.67?(m,?1H)。
Embodiment 4:2,2-two (9-(2-pyridine)-fluorenyl)-2,2 ', 2 ' '-three thiophene synthetic:
Get successively 9-hydroxyl-9 (2-pyridyl) fluorenes (0.7800 g, 3 mmol), 2,2 ', 2 ' '-dissolving of terthienyl (0.7400 g, 3 mmol), acetic acid 200 mL heated and stirred, then add the vitriol oil 4 mL and be heated to 120 ℃ of backflow 24h.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate, 17.1 %).GC-MS?(EI)?m/z?325?[M
+];1H?NMR?(400?MHz,?CDCl
3):?δ?(ppm)?8.70?(s,?1H),?8.60?(s,?1H),?7.99?(d,?
J?=?7.86,?2H),?7.70?(d,?
J?=?7.63,2H),?7.61?(d,?
J?=?7.36,?2H),?7.53?(d,?
J?=?7.16,?2H),?7.45?(m,?3H),?7.33?(m,?3H),?7.28?(d,?
J?=7.39,?1H),?7.17?(m,?5H),?7.04?(m,?2H),?6.89?(d,?
J?=?7.19,?1H),?6.71?(d,?
J?=?3.61,?1H),?6.66?(d,?
J?=?5.44,?1H),?6.62?(d,?
J?=?3.70,?1H),?6.43?(d,?
J?=?3.70,?1H),?5.84?(d,?
J?=?3.77,?1H)。
Embodiment 5:9-(2-chloroethyl)-3,6-two (9-(2-pyridine)-fluorenyl) carbazole synthetic
Get successively 9-(2-chloroethyl) carbazole (0.4600 g, 2 mmol), 9-hydroxyl-9 (2-pyridyl) fluorenes (1.0400 g, 4 mmol), acetic acid 200 mL heated and stirred dissolvings, then add the vitriol oil 4 mL and be heated to 120 ℃ of backflow 24h.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate: 16 %).GC-MS?(EI)?m/z?325?[M
+];1H?NMR?(400?MHz,?CDCl
3):?δ?(ppm)?8.62?(s,?2H),?7.78?(d,?
J?=?7.52,?2H),?7.62?(t,?
J?=?7.28,?2H),?7.47?(t,?
J?=?7.77,2H),?7.37?(t,?
J?=?7.23,?2H),?7.28?(s,?1H),?7.24?(s,?1H),?7.10?(m,?10H),?4.45?(t,?
J?=7.14,?2H),?3.71?(t,?
J?=7.15,?2H)。
Embodiment 6:3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole and 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole synthetic
Get successively N-(2-pyridyl) carbazole (1.4600 g, 6 mmol), 9-hydroxyl-9-(2-pyridyl) fluorenes (1.5500 g, 6 mmol), acetic acid 200 mL heated and stirred dissolvings, then add the vitriol oil 4 mL and be heated to 120 ℃ of 24 h that reflux.Question response is cooled to room temperature, adds about 100 mL cold water and stirs, and then adds aqueous sodium hydroxide solution to solution and is alkalescence, with dichloromethane extraction repeatedly, merges the organic phase anhydrous magnesium sulfate drying.After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating.Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product (productive rate, 3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole: 43.8%; 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole: 4.6 %).
3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole: MODI-TOF (EI) m/z 726 [M
+];
1H NMR (400 MHz, CDCl
3):
δ(ppm) 8.74 (s, 3H), 8.13 (d,
J=7.84,5H), 7.93 (t,
J=7.88,3H), 7.85 (d,
J=8.25,5H), 7.65 (d,
J=8.18,3H), 7.45 (t,
J=7.87,6H), 7.32 (m, 9H).
13C NMR (100 MHz, CDCl
3):
δ(ppm) 151.87,149.66,139.58,138.45,126.21,124.31,121.22,120.91,120.21,119.09,111.12.
3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole: GC-MS (EI) m/z 485 [M
+];
1H NMR (400 MHz, CDCl
3):
δ(ppm) 8.67 (s, 2H), 7.87 (m, 2H), 7.81 (t,
J=7.89,3H), 7.71 (m, 4H), 7.58 (d,
J=8.18,1H), 7.50 (t,
J=7.80,1H), 7.38 (m, 3H), 7.30 (t,
J=7.50,2H), 7.23 (m, 2H), 7.18 (t,
J=2.45,1H), 7.14 (m, 2H).
13C NMR (100 MHz, CDCl
3):
δ(ppm) 162.35,151.90,149.78,140.45,139.77,138.71,138.33,127.72,127.67,126.91,126.74,126.04,124.38,124.45,121.66,121.54,120.98,120.66,120.25,120.16,119.03,118.77,111.08,67.28.
Fig. 8 is to be with 3 with 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole, Fig. 9,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole, Figure 10 are with 2,2-two (9-(2-pyridine)-fluorenyl)-2,2 ', 2 ' '-three thiophene is respectively blue, green, the red three kinds of color electroluminescent spectrograms of material of main part of device; Wherein
B1,
B4,
G1,
R1All take 3-(9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole as material of main part;
B2,
G2,
R2Be material of main part with 3,6-two (9-(2-pyridine)-fluorenyl)-N-(2-pyridyl) carbazole all;
B3,
G3,
R3All be divided into material of main part with 2,2-two (9-(2-pyridine)-fluorenyl)-2,2 ', 2 ' '-three thiophene.Respectively with Firpic, Ir (ppy)
3, Ir (MDQ)
2(acac) blue, green, the red three primary colours electroluminescent device of guest materials preparation.
Claims (4)
1. pyridine fluorenes organic electrofluorescent main body luminescent material is characterized in that this material is that 9 hydrogen atom positions with fluorenes in the pyridine fluorenes class replace with different aromatic rings and make its functionalization, and it has following structure:
General formula
I
General formula
IIn, n=1 or 2, Ar are aromatic ring structure, its array structure specific as follows:
2. pyridine fluorenes organic electrofluorescent main body luminescent material according to claim 1 is characterized in that general formula
IThe compound of representative all contains pyridine fluorenes class, and the functional functional group A r of all introducings all is connected to 9 of fluorenes.
3. the preparation method of a pyridine fluorenes organic electrofluorescent main body luminescent material as claimed in claim 1 is characterized in that this preparation method is:
A. get the 2-bromopyridine and join single necked round bottom flask, low temperature stirs under dry ice acetone and nitrogen protection, getting n-Butyl Lithium slowly adds in the reactor, low-temp reaction 0.5-5 hour, get Fluorenone and inject constant pressure funnel with the THF dissolving, and add the ether dilution, be added drop-wise in the reactor, low-temp reaction 1-5 hour, normal-temperature reaction then; Use water treatment, transfer pH to be about neutrality with acetic acid, use dichloromethane extraction, the organic phase anhydrous magnesium sulfate drying, concentrated, column chromatography gets product;
B. get in 9-hydroxyl-9-(2-pyridyl) fluorenes, 2-thiotolene, the acetic acid heated and stirred dissolving adding reactor, then add the vitriol oil, be heated to back flow reaction 10-48 hour, question response is cooled to room temperature, adding cold water stirs, then add aqueous sodium hydroxide solution to solution and be alkalescence, with dichloromethane extraction repeatedly, merge the organic phase anhydrous magnesium sulfate drying; After the drying, decompress filter is also used the washed with dichloromethane siccative, gained filtrate is removed most of solvent with the Rotary Evaporators concentrating under reduced pressure, the crude product that obtains concentrating; Then column chromatography, take ethyl acetate and sherwood oil as washing composition, after the purification white solid product.
4. the application of a spiro-iridium organic electrophosphorescenmaterial material as claimed in claim 1, it is characterized in that this material is used for organic electroluminescent diode apparatus, wherein the structure of LED device is transparent anode/luminescent layer/electron injecting layer/negative electrode, wherein, luminescent layer is the Subjective and Objective system, and spiral shell fluorenes xanthene title complex is as the guest materials of luminescent layer.
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