CN102443003B - Electron transport material for organic electroluminescent devices and preparation method of electron transport material - Google Patents
Electron transport material for organic electroluminescent devices and preparation method of electron transport material Download PDFInfo
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- CN102443003B CN102443003B CN 201110272906 CN201110272906A CN102443003B CN 102443003 B CN102443003 B CN 102443003B CN 201110272906 CN201110272906 CN 201110272906 CN 201110272906 A CN201110272906 A CN 201110272906A CN 102443003 B CN102443003 B CN 102443003B
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- 0 C*=C([C@](*C=N1)Cl)C1=C(C1*)N=CC=*=C1Cl Chemical compound C*=C([C@](*C=N1)Cl)C1=C(C1*)N=CC=*=C1Cl 0.000 description 3
- CKZWMNIFBFNLQF-UHFFFAOYSA-N c1cc(cc2)c3c4c2ccc(-c2c(ccc(c5ncc6)c6-c6ccc(cc7)c8c6ccc6c8c7ccc6)c5ncc2)c4ccc3c1 Chemical compound c1cc(cc2)c3c4c2ccc(-c2c(ccc(c5ncc6)c6-c6ccc(cc7)c8c6ccc6c8c7ccc6)c5ncc2)c4ccc3c1 CKZWMNIFBFNLQF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to an electron transport material for organic electroluminescent devices and a preparation method of the electron transport material. The preparation method comprises the following steps of taking 4,7-dihalogen-1,10-phenanthroline as a starting material, and carrying out a Suzuki reaction on the starting material and arylboronic acid or arylboronate to obtain 4,7-diaryl-1,10-phenanthroline and derivates thereof as the electron transport material. The method provided by the invention has shorter synthetic route, simpler technology and higher reaction yield, obtains end-products with various types of different substituent groups, and has more easiness in material structure design and performance optimization in comparison with the conventional Skraup preparation method; meanwhile, no highly toxic materials such as arsenic acid and the like are in the reaction process, so that the reaction condition is milder, and the reaction process is safer and more environment-friendly. The preparation method provided by the invention is suitable for laboratorial preparation in gram scale and kilogram scale as well as industrial mass production in ton scale.
Description
Technical field
The invention belongs to chemosynthesis technical field, be specifically related to electron transport material for organic electroluminescence device and preparation method thereof.
Background technology
At present, used electron transport material mainly is 4,7-phenylbenzene-1 in the organic electroluminescence device (OLED), the 10-phenanthroline, and it is 4,7-diaryl-1, a kind of in the 10-phenanthroline compounds.Synthetic 4, the 7-diaryl-1 of tradition, the method for 10-phenanthroline compounds mainly are to realize (seeing the formula I) by continuous Skraup reaction, because starting raw material Ar
2COCH
2CH
2Aryl Ar among the Cl has certain limitation in the choice, can only produce in this way at present simple 4,7-phenylbenzene-1,10-phenanthroline, 4,7-diphenyl-methyl-1,10-phenanthroline and 4,7-, two benzyloxies-1, limited phenanthroline compounds such as 10-phenanthroline, this makes 4,7-diaryl-1, the structure design of 10-phenanthroline compounds has been subjected to serious restriction, and the kind kind of end product is very limited.Therefore cause the kind of this electron-like transport material single, performance also is difficult to optimize.In addition, also to use a large amount of arsenic acid poisonous reagents in the reaction process of this Skraup reaction, easily cause serious environmental to pollute.
Summary of the invention
Technical problem to be solved by this invention is to overcome in the prior art because 4,7-diaryl-1,10-phenanthroline compounds structure design difficulty causes the problem that the electron transport material kind is single, performance is difficult to optimize for organic electroluminescence device, provide a class be simple and easy to 4,7-diaryl-1,10-phenanthroline electron-like transport material.
Another object of the present invention provides the preparation method who can be used for the electron transport material in the organic electroluminescence device that a kind of preparation technology is simple, reaction conditions is gentle.
The 3rd purpose of the present invention is with a class 4,7-diaryl-1, and 10-phenanthroline compound is applied in the organic electroluminescence device as electron transport material.
For solving above technical problem, the present invention takes following technical scheme:
A kind of electron transport material for organic electroluminescence device, chemical structural formula be suc as formula shown in the II,
Wherein, Ar
1=Ar
2=following group:
Preferably, Ar
1=Ar
2=following group:
Above-mentioned electron transport material is prepared from by the Suzuki linked reaction, and reaction equation is suc as formula shown in the III:
Preferably, B (Y)
2Be boric acid or boric acid ester group.
Preferably, X is Cl, Br or I.
Preferably, the Pd valency is zeroth order in the Pd catalyzer, and further, the Pd catalyzer is selected Pd (PPh) for use
4Or Pd
2(dba)
3
The above-mentioned electron transport material of mentioning all can be applicable in the organic electroluminescence device.
In addition, the Ar in the formula II
1, Ar
2When substituting group was following several compound, they also can be used as electron transport material and are applied in the organic electroluminescence device;
Ar
1=Ar
2=following group:
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
It is multiple substituent 4 that the present invention can provide, 7-diaryl-1, and 10-phenanthroline compounds, and they are applied in the organic electroluminescence device as electron transport material; The inventive method and traditional Skraup prepared in reaction 4 of passing through, 7-diaryl-1, the method for 10-phenanthroline and derivative thereof is compared, and synthetic route is shorter, and the preparation method is simpler, and reaction yield is higher, and material structure design and performance optimization are more easy; Do not relate to highly toxic substances such as arsenic acid simultaneously in the reaction process, thus the reaction conditions milder, the safer environmental protection of reaction process.The present invention is suitable for laboratory gram level, feather weight is prepared into extensive tonne of production of industry.
Embodiment
The present invention will be further described in detail below in conjunction with specific embodiment, but be not limited to these embodiment.
The present invention select to be easy to synthesize 4,7-dihalo-1,10-phenanthroline are as starting raw material, its preparation route is suc as formula shown in the IV:
Embodiment 1
Take by weighing 4,7-, two chloro-1, and the 10-phenanthroline (2.49g 10mmol) is dissolved in 14mL toluene, pours in the reactor, methylphenylboronic acid between adding in this reactor then (2.85g, 24mmol), Pd (PPh
3)
4(231mg, 0.2mmol), Na
2CO
3(2.1g is 20mmol) with 7mL water.Said mixture was reacted 24 hours in 90 ℃ under argon shield.Add the water termination reaction in reaction solution, use ethyl acetate extraction, extraction gained organic layer is used pure washing more earlier with the saturated common salt washing, is spin-dried for finally by drying, filtration, Rotary Evaporators, namely gets crude product, and crude product is again through CH
2Cl
2/ THF (5:1) obtains analytical pure final product 3.00g, productive rate: 76% as the moving phase column chromatography.
1H?NMR(400MHz,CDCl3):δ9.22(2H,d,J=4.4Hz),7.86(2H,s),7.57(2H,d,J=4.4Hz),7.43-7.34(2H,m),7.33-7.29(6H,m),2.44(6H,s)。The reaction equation of present embodiment is shown in the formula V:
Embodiment 2
Take by weighing 4,7-, two chloro-1, the 10-phenanthroline (2.49g 10mmol) is dissolved in 14mL toluene, pours in the reactor, add in this reactor then to the phenyl phenylo boric acid (4.75g, 24mmol), Pd (PPh
3)
4(231mg, 0.2mmol), Na
2CO
3(2.1g is 20mmol) with 7mL water.Said mixture was reacted 24 hours in 90 ℃ under argon shield.Add the water termination reaction in reaction solution, use ethyl acetate extraction, extraction gained organic layer is used pure washing more earlier with the saturated common salt washing, is spin-dried for finally by drying, filtration, Rotary Evaporators, namely gets crude product, and crude product is again through CH
2Cl
2/ THF (5:1) obtains analytical pure final product 3.00g, productive rate: 76% as the moving phase column chromatography.
1H?NMR(400MHz,CDCl3):δ9.27(2H,d,J=4.8Hz),7.97(2H,s),7.77(4H,m,J=4.8Hz),7.69(4H,m,J=7.6Hz),7.65-7.62(6H,m),7.52-7.48(4H,m),7.42-7.39(2H,m)。The reaction equation of present embodiment is shown in the formula VI:
Embodiment 3
Take by weighing 4,7-, two chloro-1, the 10-phenanthroline (2.49g 10mmol) is dissolved in 14mL toluene, pours in the reactor, add in this reactor then 1-naphthyl phenylo boric acid (4.13g, 24mmol), Pd (PPh
3)
4(231mg, 0.2mmol), Na
2CO
3(2.1g is 20mmol) with 7mL water.Said mixture was reacted 24 hours in 90 ℃ under argon shield.Add the water termination reaction in reaction solution, use ethyl acetate extraction, extraction gained organic layer is used pure washing more earlier with the saturated common salt washing, is spin-dried for finally by drying, filtration, Rotary Evaporators, namely gets crude product, and crude product is again through CH
2Cl
2/ THF (5:1) obtains analytical pure final product 2.6g, productive rate: 60% as the moving phase column chromatography.
1H NMR (400MHz, CDCl
3): δ 9.35 (2H, d, J=4.4Hz), 7.95-7.89 (4H, m), 7.66 (2H, d, J=4.8Hz), 7.57-7.53 (2H, m), 7.48-7.43 (4H, m), 7.37-7.29 (4H, m), 7.21 (1H, s), 7.19 (1H, s) reaction equation of present embodiment is shown in the formula VII:
Embodiment 4
Take by weighing 4,7-, two chloro-1, the 10-phenanthroline (2.49g 10mmol) is dissolved in 14mL toluene, pours in the reactor, add in this reactor then 1-pyrene boric acid (5.50g, 24mmol), Pd (PPh
3)
4(231mg, 0.2mmol), Na
2CO
3(2.1g is 20mmol) with 7mL water.Said mixture was reacted 24 hours in 90 ℃ under argon shield.Add the water termination reaction in reaction solution, use ethyl acetate extraction, extraction gained organic layer is used pure washing more earlier with the saturated common salt washing, is spin-dried for finally by drying, filtration, Rotary Evaporators, namely gets crude product, and crude product is again through CH
2Cl
2/ THF (5:1) obtains analytical pure final product 4.06g, productive rate: 70% as the column chromatography of moving phase.The reaction equation of present embodiment is shown in the formula VIII:
Embodiment 5
Take by weighing 4,7-, two chloro-1, the 10-phenanthroline (2.49g 10mmol) is dissolved in 14mL toluene, pours in the reactor, add in this reactor then 3-pyridine boric acid pinacol ester (4.92g, 24mmol), Pd (PPh
3)
4(231mg, 0.2mmol), Na
2CO
3(2.1g is 20mmol) with 7mL water.Said mixture was reacted 24 hours in 90 ℃ under argon shield.Add the water termination reaction in reaction solution, use ethyl acetate extraction, extraction gained organic layer is used pure washing more earlier with the saturated common salt washing, is spin-dried for finally by drying, filtration, Rotary Evaporators, namely gets crude product, and crude product is again through CH
2Cl
2/ THF (5:1) obtains analytical pure final product 2.60g, productive rate: 78% as the column chromatography of moving phase.The reaction equation of present embodiment is shown in the formula IX:
Embodiment 6
Embodiment 5 prepared compounds are used for the making (with traditional BCP material compared) of green device as electric transmission hole blocking layer (ETL-HBL), the structure of green device is ITO/NPB (40nm)/mcp:Ir (ppy) 3 (10wt%30nm)/ETL-HBL(10nm) Alq3 (30nm)/LiF (1nm)/Al, the luminosity that experiment records this green device maximum is 18650cd m-2 (BCP is 11065cd m-2), as seen, adopt embodiment 5 prepared compounds as electron transport material the luminous efficiency of green device is improved a lot.Embodiment 5 prepared compounds are because 1,4,7 of 10-phenanthrolines have been introduced electrophilic pyridine group, have effectively reduced the LUMO value of material, thereby further having improved electric transmission and the electronics injectability of material, this is conducive to the improvement of luminescent device performance.
More than the present invention has been done detailed description; its purpose is to allow the personage that is familiar with this art can understand content of the present invention and is implemented; can not limit protection scope of the present invention with this; the equivalence that all spirit according to the present invention are done changes or modifies, and all should be encompassed in protection scope of the present invention.
Claims (5)
1. electron transport material that is used for organic electroluminescence device is characterized in that: the chemical structural formula of described electron transport material is suc as formula shown in the II,
Wherein, Ar
1=Ar
2=following group:
（9）
2. the preparation method of the described electron transport material of claim 1, it is characterized in that: described electron transport material is prepared from by the Suzuki linked reaction, and reaction equation is suc as formula shown in the III:
Wherein: B (Y)
2Be boric acid or boric acid ester group; X is Cl, Br or I.
3. preparation method according to claim 2, it is characterized in that: the Pd valency is zeroth order in the Pd catalyzer.
4. preparation method according to claim 3, it is characterized in that: the Pd catalyzer is Pd (PPh)
4Or Pd
2(dba)
3
5. the application of the described electron transport material of claim 1 in organic electroluminescence device.
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| CN103992315B (en) * | 2014-05-07 | 2016-01-20 | 华东师范大学 | Dibenzo [c, i] [1,10] o-phenanthroline and derivative thereof and preparation method |
| CN104945402A (en) * | 2015-06-16 | 2015-09-30 | 上海应用技术学院 | 4,7 substituted-1,10-phenanthroline derivative and preparation method thereof |
| KR102430678B1 (en) * | 2019-03-08 | 2022-08-09 | 주식회사 엘지화학 | Compound and organic light emitting device comprising the same |
| KR20220081022A (en) * | 2020-12-08 | 2022-06-15 | 엘지디스플레이 주식회사 | Organic compound, and Organic light emitting diode and Organic light emitting device including the same |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2161272A1 (en) * | 2008-09-05 | 2010-03-10 | Basf Se | Phenanthrolines |
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| JP5628830B2 (en) * | 2008-12-22 | 2014-11-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーＥ．Ｉ．Ｄｕ Ｐｏｎｔ Ｄｅ Ｎｅｍｏｕｒｓ Ａｎｄ Ｃｏｍｐａｎｙ | Electronic devices containing phenanthroline derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2161272A1 (en) * | 2008-09-05 | 2010-03-10 | Basf Se | Phenanthrolines |
Non-Patent Citations (1)
| Title |
|---|
| Peter C. Alford，等.Luminescent Metal Complexes. Part 5.Luminescence Properties of Ring-substituted 1,10-Phenanthroline Tris-complexes of Ruthenium(II).《J. CHEM. SOC. PERKIN TRANS. II》.1985,705-709. * |
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