CN101144012A - Anthracene electroluminescence material containing cavity transmission group and preparation method thereof - Google Patents
Anthracene electroluminescence material containing cavity transmission group and preparation method thereof Download PDFInfo
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- CN101144012A CN101144012A CNA2007101396379A CN200710139637A CN101144012A CN 101144012 A CN101144012 A CN 101144012A CN A2007101396379 A CNA2007101396379 A CN A2007101396379A CN 200710139637 A CN200710139637 A CN 200710139637A CN 101144012 A CN101144012 A CN 101144012A
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Abstract
An anthracene electroluminescent material with hole-transporting moieties is 9,10-di-(4'-N, N-diphenyl-benzenamine)anthracene organic compound, the preparation method of which includes the following steps: (1) under ultrasound irradiation, chloro triphenylamine, triisopropyl borate ester and magnesium powder in THF are initiated by molecular iodine to react for 20-40 min, and then hydrolyzed under acidic condition to obtain mono-substituted triphenylamine boric acid; (2) using palladium acetate as catalyst and triphenyl phosphine as ligands, mono-substituted triphenylamine boric acid and 9, 10-dibromo-anthracene in toluene are under alkaline condition to obtain the luminescent material. The invention bring typical hole-transporting moieties triphenylamine into anthracene luminophor, thereby to break through conventional simple modification to anthracene main body material compound, and realize a greater extent regulation of electroluminescent material carrier transmission property, so as to provide novel electroluminescent material for realization of high quantum yield and electron mobility of the light-emitting device.
Description
Technical field
The present invention relates to luminescent material, specifically belong to a kind of anthracene electroluminescence material that contains cavity transmission group and preparation method thereof.
Background technology
Along with the develop rapidly of 21st century Materials science, information science, life science, its subject crossing point photon-electronics material has been subjected to people's extensive concern.And organic electroluminescent (Organic electroluminescence) material with the optical information acknowledge signal has obtained using widely and developing in fields such as optical information demonstration, space instrument, military field, life system, safety detection, medical diagnosiss in photon-electronics material.Anthracene is the electroluminous organic small molecular material of studying the earliest, people such as Pope (Pope M, Kallmann H, Magnante P.Electroluminescence in organic crystal[J] .J ChemPhys, 1963, be that the both sides of the anthracene single crystal sheet of 10-20 μ m have observed luminescence phenomenon when adding the volts DS of 400V 38:2042-2943), afterwards at thickness, people have also carried out simple modification research to the monocrystalline anthracene, improve its luminescent properties.From present development, to the requirement of electroluminescent material, except high luminous efficiency and brightness, also require its have good physical properties as: stability, film-forming properties wait to satisfy to make the requirement of thin-film device.In addition, as electroluminescent organic material, also require to have good carrier transmission performance, i.e. electronics and the hole transmission in this material preferably can reach certain balance, the luminescent layer that is compounded in of current carrier is taken place, thereby send needed light.Organic micromolecule compound has that chemical structure is easy to adjust, carrier mobility height and compound purity height, can obtain purer advantages such as coloured light, yet, because most of electroluminous organic small molecular materials are unipolar, only have one of electric transmission and hole transport character, and the organic molecule of impartial hole and electric transmission character seldom.If, will cause the quencher of carrier transport, reduce the luminous efficiency and the brightness of device with the luminescent material of this unipolar organism as single layer device.Address this problem optimal method and be to design and synthesize the twinkler of big conjugated system and have the carrier transport functional group and include in the same material compound molecule, go to regulate the carrier transport ratio, reduce film thickness.Therefore design and prepare the triphenylamine functional group with good hole transport performance is included in the anthracene twinkler, come the anthracene luminophor is effectively modified, and then improving its luminous efficiency, it is aim of the present invention that the optimization luminescent properties obtains novel luminous organic material compound molecule.
Summary of the invention
The object of the present invention is to provide a kind of quantum yield and electronic mobility high contain anthracene electroluminescence material of cavity transmission group and preparation method thereof.
A kind of anthracene electroluminescence material that contains cavity transmission group provided by the invention, it is 9,10-two-(4 '-N, N-phenylbenzene aniline) anthracene organic compound, its structural formula is:
The present invention contains the preparation method of the anthracene electroluminescence material of cavity transmission group, comprises the steps:
1), under the ultrasonic wave effect, for triphenylamine, tri-isopropylborate and magnesium powder, THF makes solvent by monochloro, elemental iodine is an initiator, 25 ℃～50 ℃ down reactions 20～40 minutes, hydrolysis makes single triphenylamine boric acid (II) that replaces under acidic conditions then;
2), by single triphenylamine boric acid and 9 that replaces, the 10-dibromoanthracene, in toluene, palladium is a catalyzer, triphenyl phosphorus is made part, and at 90 ℃～110 ℃, alkaline condition reacted 24～72 hours down, make 9,10-two-(4 '-N, N-phenylbenzene aniline) anthracene compound (I);
In the described step 1): reactant consumption mol ratio is a monochloro for triphenylamine: tri-isopropylborate: magnesium powder=1: 1.0～1.2: 1.2～1.5; Ultrasonic power is 150W～200W;
Described step 2) in: reactant consumption mol ratio is single triphenylamine boric acid that replaces: 9, and 10-dibromoanthracene: sodium acetate=2.0～2.5: 1: 2.0～3.0; The mol ratio of catalyzer and part is Pd (OAc)
2: PPh
3=1: 3.5～5.5.
Compared with prior art the present invention has following characteristics: the present invention includes typical cavity transmission group triphenylamine in the anthracene twinkler in, broken through traditional simple modification to anthracene material of main part compound, realized adjusted electroluminescent material carrier transmission performance more, thereby for realizing that quantum yield and the high luminescent device of electronic mobility provide new electroluminescent material; Preparation method of the present invention, equipment is simple, and is easy to operate, gained material purity height.
Embodiment
Embodiment 1
In the single port circle Florence flask of 100mL, add 2.55ml (11mmol) three and replace the sec.-propyl boric acid ester, 2.791g (10mmol) monochloro is for triphenylamine, 0.288g (12mmol) magnesium powder, 50mL through potassium hydroxide exsiccant tetrahydrofuran (THF) and a little iodine as initiator, load onto reflux condensing tube, in ultrasound reactor under 40 ℃, 175W ultrasonic power, ultrasonic radiation 30min, after reaction finishes, hydrochloric acid conditioned reaction liquid with 2mol/L shows slightly acid, stirs and moments later tells organic layer, and the adularescent precipitation is separated out.Water layer is with the extracted with diethyl ether twice of 30mL, with the organic layer that merges through washing, after dry back rotary evaporation removes and desolvates thick product, the pure product of thick product water recrystallization purifying.Productive rate is 63%,
1H-NMR (d
6-DMSO, ppm) δ: 7.12-6.84 (m, 6H, in the triphenylamine N between the position hydrocarbon), 6.76～6.33 (the adjacency pair position of N is hydrocarbon in the triphenylamine for m, 8H), the hydrogen on the boric acid is by deuterium generation; Elemental analysis:Calcd (%) C
18H
16BNO
2(289.13) C, 74.77; H, 5.58; N, 4.84; O, 11.07.Found:C, 73.96; H, 5.73; N, 5.04; O, 10.67; FTIR (KBr, cm
-1): 3392,3104,1622,1591,1519,1475,1267,1145,843.
In the there-necked flask of 100mL, add 0.112g (0.5mmol) Carbon Dioxide palladium; 0.524g (2.0mmol) triphenylphosphine; 8.4g (25.0mmol) 9; 10-two-bromine anthracene; 4.0g (50mmol) sodium-acetate, single triphenylamine boric acid, the 50mL dry toluene of replacing of 14.46g (50mmol); nitrogen protection is heated to 110 ℃ of following stirring reaction 48h.Reaction finishes, and is cooled to room temperature, and reactant is poured in the frozen water, has the precipitation of yellow-white to separate out.Filter, drying, use anhydrous alcohol solution, refilter, dry single yellow solid, single yellow solid column chromatography is separated (eluent: sherwood oil: ethyl acetate=8: 1), must single yellow solid crystallization, productive rate about 30.4%.
1H-NMR (d
6-DMSO, ppm) δ: 7.86-7.55 (on the anthracene nucleus hydrocarbon), δ: 7.32-6.91 (m, 6H, in the triphenylamine N between the position hydrocarbon), 6.80～6.43 (the adjacency pair position of N is hydrocarbon in the triphenylamine for m, 8H); Elemental analysis:Calcd (%) C
50H
36N
2(664.83) C, 90.33; H, 5.46; Found:C, 90.67; H, 5.51; FTIR (KBr, cm
-1): 3112,1632,1597,1562,1495,1277,814.
Embodiment 2
In the single port circle Florence flask of 100mL, add 2.78ml (10mmol) three and replace the sec.-propyl boric acid ester, 2.791g (10mmol) monochloro is for triphenylamine, 0.36g (15mmol) magnesium powder, 50mL through potassium hydroxide exsiccant tetrahydrofuran (THF) and a little iodine as initiator, load onto reflux condensing tube, in ultrasound reactor under 30 ℃, 200W ultrasonic power, ultrasonic radiation 30min, after reaction finishes, hydrochloric acid conditioned reaction liquid with 2mol/L shows slightly acid, stirs and moments later tells organic layer, and the adularescent precipitation is separated out.Water layer is with the extracted with diethyl ether twice of 30mL, with the organic layer that merges through washing, after dry back rotary evaporation removes and desolvates thick product, the pure product of thick product water recrystallization purifying.Productive rate is 49%,
1H-NMR (d
6-DMSO, ppm) δ: 7.12-6.84 (m, 6H, in the triphenylamine N between the position hydrocarbon), 6.76～6.33 (the adjacency pair position of N is hydrocarbon in the triphenylamine for m, 8H), the hydrogen on the boric acid is by deuterium generation; Elemental analysis:Calcd (%) C
18H
16BNO
2(289.13) C, 74.77; H, 5.58; N, 4.84; O, 11.07.Found:C, 73.96; H, 5.73; N, 5.04; O, 10.67; FTIR (KBr, cm
-1): 3392,3104,1622,1591,1519,1475,1267,1145,843.
According to the method preparation 9 of example 1,10-two-(4 '-N, N-phenylbenzene aniline) anthracene compound (I).
Embodiment 3
According to the single triphenylamine boric acid (II) that replaces of the method preparation of example 1.
In the there-necked flask of 100mL, add 0.112g (0.5mmol) Carbon Dioxide palladium; 0.665g (2.5mmol) triphenylphosphine; 8.4g (25.0mmol) 9; 10-two-bromine anthracene; 4.0g (50mmol) sodium-acetate, single triphenylamine boric acid, the 50mL dry toluene of replacing of 15.91g (50mmol); nitrogen protection is heated to 90 ℃ of following stirring reaction 48h.Reaction finishes, and is cooled to room temperature, and reactant is poured in the frozen water, has the precipitation of yellow-white to separate out.Filter, drying, use anhydrous alcohol solution, refilter, dry single yellow solid, single yellow solid column chromatography is separated (eluent: sherwood oil: ethyl acetate=8: 1), must single yellow solid crystallization, productive rate about 26.3%.
1H-NMR (d
6-DMSO, ppm) δ: 7.86-7.55 (on the anthracene nucleus hydrocarbon), δ: 7.32-6.91 (m, 6H, in the triphenylamine N between the position hydrocarbon), 6.80～6.43 (the adjacency pair position of N is hydrocarbon in the triphenylamine for m, 8H); Elemental analysis:Calcd (%) C
50H
36N
2(664.83) C, 90.33; H, 5.46; Found:C, 90.67; H, 5.51; FTIR (KBr, cm
-1): 3112,1632,1597,1562,1495,1277,814.
Claims (2)
1. an anthracene electroluminescence material that contains cavity transmission group is characterized in that, it is 9,10-two-(4 '-N, N-phenylbenzene aniline) anthracene organic compound, and its structural formula is:
2. the preparation method of luminescent material as claimed in claim 1 is characterized in that, comprises the steps:
1), under the ultrasonic wave effect, for triphenylamine, tri-isopropylborate and magnesium powder, THF makes solvent by monochloro, elemental iodine is an initiator, 25 ℃～50 ℃ down reactions 20～40 minutes, hydrolysis makes single triphenylamine boric acid (II) that replaces under acidic conditions then;
2), by single triphenylamine boric acid and 9 that replaces, the 10-dibromoanthracene, in toluene, palladium is a catalyzer, triphenyl phosphorus is made part, and at 90 ℃～110 ℃, alkaline condition reacted 24～72 hours down, make 9,10-two-(4 '-N, N-phenylbenzene aniline) anthracene compound (I);
In the described step 1): reactant consumption mol ratio is a monochloro for triphenylamine: tri-isopropylborate: magnesium powder=1: 1.0～1.2: 1.2～1.5; Ultrasonic power is 150W～200W;
Described step 2) in: reactant consumption mol ratio is single triphenylamine boric acid that replaces: 9, and 10-dibromoanthracene: sodium acetate=2.0～2.5: 1: 2.0～3.0; The mol ratio of catalyzer and part is Pd (OAc)
2: PPh
3=1: 3.5～5.5.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102225881A (en) * | 2011-04-28 | 2011-10-26 | 西安近代化学研究所 | 9,9<,>-bisanthracene derivative and preparation method thereof |
| CN102391478A (en) * | 2011-09-20 | 2012-03-28 | 忻州师范学院 | Water-soluble polymer with anthracene functional group and preparation method thereof |
| JP2012508782A (en) * | 2008-11-17 | 2012-04-12 | ユニベルシテ ドゥ ニース ソフィア アンティポリ | Process for preparing boronic acids and boronic esters in the presence of magnesium metal |
| CN103382181A (en) * | 2013-07-09 | 2013-11-06 | 京东方科技集团股份有限公司 | Multiaryl-substituted pyrimidine derivative, its preparation method, organic electroluminescent device, and organic electroluminescent display device |
| CN110041374A (en) * | 2019-05-07 | 2019-07-23 | 西安凯立新材料股份有限公司 | A kind of preparation method of palladium complex |
-
2007
- 2007-10-26 CN CNA2007101396379A patent/CN101144012A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012508782A (en) * | 2008-11-17 | 2012-04-12 | ユニベルシテ ドゥ ニース ソフィア アンティポリ | Process for preparing boronic acids and boronic esters in the presence of magnesium metal |
| CN102225881A (en) * | 2011-04-28 | 2011-10-26 | 西安近代化学研究所 | 9,9<,>-bisanthracene derivative and preparation method thereof |
| CN102225881B (en) * | 2011-04-28 | 2014-12-10 | 西安近代化学研究所 | 9,9<,>-bisanthracene derivative and preparation method thereof |
| CN102391478A (en) * | 2011-09-20 | 2012-03-28 | 忻州师范学院 | Water-soluble polymer with anthracene functional group and preparation method thereof |
| CN103382181A (en) * | 2013-07-09 | 2013-11-06 | 京东方科技集团股份有限公司 | Multiaryl-substituted pyrimidine derivative, its preparation method, organic electroluminescent device, and organic electroluminescent display device |
| CN103382181B (en) * | 2013-07-09 | 2015-05-20 | 京东方科技集团股份有限公司 | Multiaryl-substituted pyrimidine derivative, its preparation method, organic electroluminescent device, and organic electroluminescent display device |
| US9716235B2 (en) | 2013-07-09 | 2017-07-25 | Boe Technology Group Co., Ltd. | 9,10-bis[2-(p-substituted phenyl)pyrimidin-4-yl] anthracene compounds, methods of preparing the same, organic electroluminescent devices and organic electroluminescent display apparatus |
| CN110041374A (en) * | 2019-05-07 | 2019-07-23 | 西安凯立新材料股份有限公司 | A kind of preparation method of palladium complex |
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Open date: 20080319 |