CN1560038A - Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof - Google Patents
Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof Download PDFInfo
- Publication number
- CN1560038A CN1560038A CNA2004100165655A CN200410016565A CN1560038A CN 1560038 A CN1560038 A CN 1560038A CN A2004100165655 A CNA2004100165655 A CN A2004100165655A CN 200410016565 A CN200410016565 A CN 200410016565A CN 1560038 A CN1560038 A CN 1560038A
- Authority
- CN
- China
- Prior art keywords
- compound
- electroluminescent
- fluorescence
- electrophosphorescence
- maximum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a new electrophosphorescent or electrofluorescent substituted benzoheterocyclic compound. It contains phenylamine and heterocyclic functional groups, and has good cavity transmission ability and luminescent (phosphorescence or fluorescence) property. As it is applied to electroluminescent devices, its maximum luminescent wavelengths are in 408-480 nm (show blue light) and 570-630 nm (show salmon pink light), respectively; at driving voltage of 20V, its maximum radiances are 4500 cd/sq m and 4300 cd/sq m, respectively.
Description
Technical field
The present invention relates to the replacement benzo-heterocycle compound of electroluminescent phosphorescence or fluorescence, belong to field of organic electroluminescent materials.
Background technology
Compare with liquid-crystal display, organic electroluminescence device (OLED) is the state-of-the-art technique of display of generally acknowledging at present.It has overcome the shortcoming of liquid-crystal display, and low voltage direct drive, active illuminating, visual angle are big, flexible, the fast big area of response speed shows, luminous color is complete and low cost and other advantages but have.Thereby nearly all in the world associated major company all drops into a large amount of man power and materials and develops novel electroluminescent device, and competition is day by day from thermalization.In organic electroluminescence device (OLED), the performance of electroluminescent material plays very important effect to the luminous efficiency of device, and therefore, the research of relevant electroluminescent material is in the ascendant.
Summary of the invention
The objective of the invention is to the replacement benzo-heterocycle compound that to disclose a kind of novel electroluminescent material be electroluminescent phosphorescence or fluorescence.
Technical scheme:
The structure that said electroluminescent phosphorescence of the present invention or fluorescence replace benzo-heterocycle compound is shown below:
Or
In the formula: X is S, O or N; R
1, R
2Be C
1～C
7Alkyl in a kind of;
M is metal iridium (Ir), palladium (Pd) or europium (Eu); N is the integer between 1～6.
Preferred R
1, R
2A kind of in methyl, ethyl, phenyl and the tolyl; Preferred R
1, R
2Be phenyl.The synthetic of above-claimed cpd is such:
Phenyl aldehyde or benzoic ether with para-orientation are starting raw material, behind the aniline cyclization that replaces with the ortho position compound (1), the compound (2) behind compound (1) and the metal complex.Wherein the aniline of the benzoic ether of the phenyl aldehyde of para-orientation, para-orientation and ortho position replacement is commercially available product.
Said compound of the present invention (1) and compound (2) all can adopt prior art to make electroluminescent device, wherein make its maximum emission wavelength of electroluminescent device between 408～480nm by compound (1), be blue light, maximum luminance is 4300cd/m under driving voltage 20V
2And make its maximum emission wavelength of electroluminescent device at 570～630nm by compound (2), and being orange red light, maximum luminance is 4500cd/m under driving voltage 20V
2Electroluminescent phosphorescence that the present invention designs and synthesizes or fluorescence replace benzo-heterocycle compound to have good cavity transmission ability and luminous (phosphorescence or fluorescence) performance.
Embodiment:
Further illustrate the present invention below in conjunction with example, but example does not limit protection scope of the present invention.
Embodiment 1
Synthesizing of 4-benzothiazolyl-2-(N, N-dimethyl) aniline
In flask, add 2.0g 4-dimethylaminobenzaldehyde, 3ml near amino thiophenols, 15ml methyl alcohol: the mixing solutions of benzene=1: 2.Stir, reaction system is the dark brown red clear solution.React 36h under the room temperature, have yellow mercury oxide to generate.Suction filtration is with methyl alcohol drip washing filter cake.With acetone recrystallization, get light yellow needle-like crystal.Suction filtration, drying, weight are 1.95g, productive rate 51%, 157～159 ℃ of fusing points.
1H-NMR(CDCl
3)：3.06(s，6H)，6.75(d，J＝8.88Hz，2H)，7.31(t，J＝0.8Hz，J＝0.86Hz，1H)，7.44(t，J＝0.96Hz，J＝0.93Hz，1H)，7.84(d，J＝7.89Hz，1H)，7.97(d，2H)，7.99(d，1H).EI?m/e：254(100％)。
Maximal ultraviolet-visible absorbance wavelength is 356nm (tetrahydrofuran solution), and log ε is 4.66.Blue-fluorescence, maximum emission wavelength are 408nm.
Embodiment 2
4-benzothiazolyl-2-[N, N-two (4-methyl) phenyl] aniline synthetic
In flask, add 1.0g 4-(two p-methylphenyls) aminobenzaldehyde, the 0.5g near amino thiophenols, 15ml methyl alcohol: the mixing solutions of benzene=1: 2, stir, reaction system is shallow yellow transparent solution.React 72h under the room temperature.The rotary evaporation solvent gets product (deep yellow solid) after the column chromatography for separation.Drying, weight are 0.76g, productive rate 57%, 135～139 ℃ of fusing points.
1H-NMR(CDCl
3)：2.34(s，6H)，7.03(d，J＝8.64Hz，2H)，7.06(d，J＝8.24Hz，4H)，7.12(d，J＝8.15Hz，4H)，7.33(t，1H)，7.45(t，1H)，7.86(d，1H)，7.88(d，J＝8.8Hz，2H)，8.00(d，1H).EI?m/e：406(100％)。
Maximal ultraviolet-visible absorbance wavelength is 379nm (tetrahydrofuran solution), and log ε is 3.82.Blue-fluorescence, maximum emission wavelength are 476nm.
Embodiment 3
Synthesizing of 4-benzothiazolyl-2-(N, N-phenylbenzene) aniline
In flask, add 0.5g 4-diphenyl amino phenyl aldehyde, the 0.2g near amino thiophenols, 15ml methyl alcohol: the mixing solutions of benzene=1: 2, normal temperature stirs down, and reaction system is pale brown look clear solution.Reaction 48h.The rotary evaporation solvent gets yellow chip solid behind the column chromatography for separation product.Drying, weight are 0.24g, productive rate 43%, 124～126 ℃ of fusing points.
1H-NMR(CDCl
3)：7.11(d，J＝8.58Hz，2H)，7.12(t，2H)，7.17(d，J＝7.68Hz，4H)，7.31(t，4H)，7.34(t，1H)，7.46(t，1H)，7.87(d，J＝7.88Hz，1H)，7.92(d，2H)，8.02(d，J＝8.13Hz，1H).EI?m/e：378(100％)。
Maximal ultraviolet-visible absorbance wavelength is 372nm (tetrahydrofuran solution), and log ε is 3.80.Blue-fluorescence, maximum emission wavelength are 456nm.
Embodiment 4
Synthesizing of 4-benzoxazolyl-2-(N, N-dimethyl) aniline
In round-bottomed flask, add 2.0g (dimethylamino)-ethyl benzoate, 1.13g Ortho-Aminophenol and 30mL polyphosphoric acid (PPA).Argon shield is heated to about 250 ℃, reaction 4h.After the cooling, be diluted to solid with water and separate out.Filter, filter cake is inserted 10%Na
2CO
3In the aqueous solution, the powerful stirring left standstill 30min, and suction filtration gets thick product.Drying, 95% ethyl alcohol recrystallization gets target compound (pale brown look needle-like crystal).EI?m/e：238(100％)。
Embodiment 5
Synthesizing of 4-benzimidazolyl--2-(N, N-dimethyl) aniline
In round-bottomed flask, add 2.0g (dimethylamino)-ethyl benzoate, 1.12g O-Phenylene Diamine and 30mL polyphosphoric acid (PPA).Argon shield is heated to about 250 ℃, reaction 4h.After the cooling,, separate out solid with the water dilution.Filter, filter cake is inserted 10%Na
2CO
3In the aqueous solution, the powerful stirring left standstill 30min, and suction filtration gets thick product.Drying, 95% ethyl alcohol recrystallization gets target compound (pale brown look needle-like crystal).EI?m/e：237(100％)。
Embodiment 6
The complex compound of 4-benzothiazolyl-2-(N, N-phenylbenzene) aniline and metal iridium is synthetic
In flask, add the 50mg tri acetylacetonato and close iridium [Ir (acac)
3], 160mg part 4-benzothiazolyl-2-(N, N-phenylbenzene) aniline is selected the higher solvent of boiling point (as glycerine or ethylene glycol) 25mL for use.About 120 ℃ of 2h that bleed, argon shield, stirring, backflow 24h.Reaction is chilled to room temperature after finishing naturally, has a small amount of orange-yellow precipitation to separate out.Add entry, standing over night has precipitation to separate out.Suction filtration behind the filtration cakes torrefaction, gets orange-yellow needle-like crystal after the column chromatography for separation.ESI?m/e：1324(100％)。
Maximal ultraviolet-visible absorbance wavelength is 421nm (tetrahydrofuran solution), and orange-yellow fluorescence, maximum emission wavelength are 565nm (tetrahydrofuran solution).Its solid state powder maximum emission wavelength is 578nm, sends out coloured light orange.
Embodiment 7
4-benzothiazolyl-2-[N, N-two (4-methyl) phenyl] complex compound of aniline and metal iridium is synthetic
In flask, add the 50mg tri acetylacetonato and close iridium [Ir (acac)
3], 190mg part 4-benzothiazolyl-2-[N, N-two (4-methyl) phenyl] aniline, select the higher solvent of boiling point (glycerine or ethylene glycol) 25mL for use.About 120 ℃ of 2h that bleed, argon shield, stirring, backflow 24h.Reaction is chilled to room temperature after finishing naturally, has a small amount of salmon precipitation to separate out.Add entry, standing over night has precipitation to separate out.Suction filtration, behind the filtration cakes torrefaction, column chromatography for separation (developping agent be methylene dichloride/hexanaphthene=1: 1).Get orange red needle-like crystal.ESI?m/e：[M+Na]1431(100％)。
Maximal ultraviolet-visible absorbance wavelength is 426nm (tetrahydrofuran solution), and fluorescent red-orange, maximum emission wavelength are 570nm (tetrahydrofuran solution).Its solid state powder maximum emission wavelength is 622nm, sends out orange-red light.
Embodiment 8
Do to make electroluminescent device as electroluminescent material with the compound of embodiment 2, the layers of material and the structural parameter of electroluminescent device are as follows:
Glass substrate //ITO//CuPc (10nm)/TPD (10nm)/luminescent material (30nm) //LiF (7nm)/AlLi;
The element manufacturing program is as follows: matrix adopts the ito glass of ultrasonic cleansing, and its resistance is 20 Ω/, the negative electrode (0.28cm of device
2) and organic thin film layer be to adopt vacuum vapour deposition coating (vacuum tightness is 1 * 10
-7Torr), wherein TPD is N, N '-triphenyl diamines, and CuPc is a copper phthalocyanine, plays the hole transport effect.The thickness of device is measured with step instrument (Tenco Alpha-step500), and the electroluminescent spectrogram is to measure with PTI QMl luminoscope.When driving voltage is 20V, the maximum emission wavelength in its electroluminescent peak between 408～480nm, blue light-emitting, maximum luminance is 4300cd/m under driving voltage 20V
2, device through 48 hours continuously luminous after, luminosity still can maintain 100cd/m
2More than.
Embodiment 9
Do to make electroluminescent device as electroluminescent material with the compound of embodiment 6, the layers of material and the structural parameter of electroluminescent device are as follows:
Glass substrate //ITO//luminescent material (83nm) //LiF (7nm)/AlLi;
Element manufacturing program and test similar embodiment 8.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak sent out light orange red between 570-630nm, and maximum luminance is 4500cd/m
2, device through 48 hours continuously luminous after, luminosity still can maintain l00cd/m
2More than.
Claims (3)
1, electroluminescent phosphorescence or fluorescence replace benzo-heterocycle compound, and its structure is shown below:
Or
In the formula: X is S, O or N; R
1, R
2Be C
1～C
7Alkyl in a kind of;
M is metal iridium, palladium or europium; N is the integer between 1～6.
2, compound as claimed in claim 1 is characterized in that, wherein R
1, R
2A kind of in methyl, ethyl, phenyl and the tolyl.
3, compound as claimed in claim 2 is characterized in that, wherein R
1, R
2Be phenyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016565 CN1259312C (en) | 2004-02-26 | 2004-02-26 | Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410016565 CN1259312C (en) | 2004-02-26 | 2004-02-26 | Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1560038A true CN1560038A (en) | 2005-01-05 |
| CN1259312C CN1259312C (en) | 2006-06-14 |
Family
ID=34440537
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410016565 Expired - Fee Related CN1259312C (en) | 2004-02-26 | 2004-02-26 | Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1259312C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1953844A1 (en) * | 2005-10-31 | 2008-08-06 | Nippon Steel Chemical Co., Ltd. | Organic electroluminescent device |
| CN102050798A (en) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2'-hydroxylphenyl)-benzothiazole derivative luminescent materials |
| JP2013028597A (en) * | 2011-06-24 | 2013-02-07 | Semiconductor Energy Lab Co Ltd | Triarylamine compound, light-emitting element, light-emitting device, electronic equipment and lighting device |
| CN104140400A (en) * | 2014-07-15 | 2014-11-12 | 江阴市天顺彩印有限公司 | Green fluorescent compound and synthetic method and application of green fluorescent compound |
-
2004
- 2004-02-26 CN CN 200410016565 patent/CN1259312C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1953844A1 (en) * | 2005-10-31 | 2008-08-06 | Nippon Steel Chemical Co., Ltd. | Organic electroluminescent device |
| EP1953844A4 (en) * | 2005-10-31 | 2009-11-25 | Nippon Steel Chemical Co | Organic electroluminescent device |
| CN102050798A (en) * | 2010-12-07 | 2011-05-11 | 吉林大学 | 2-(2'-hydroxylphenyl)-benzothiazole derivative luminescent materials |
| JP2013028597A (en) * | 2011-06-24 | 2013-02-07 | Semiconductor Energy Lab Co Ltd | Triarylamine compound, light-emitting element, light-emitting device, electronic equipment and lighting device |
| US9525143B2 (en) | 2011-06-24 | 2016-12-20 | Semiconductor Energy Laboratory Co., Ltd. | Triarylamine compound, light-emitting element, light-emitting device, electronic device, and lighting device |
| CN104140400A (en) * | 2014-07-15 | 2014-11-12 | 江阴市天顺彩印有限公司 | Green fluorescent compound and synthetic method and application of green fluorescent compound |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1259312C (en) | 2006-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI468489B (en) | Organic electroluminescent element compounds and organic electroluminescent elements | |
| CN100509827C (en) | Electroluminescent material | |
| TWI429652B (en) | Organic metal compound, organic electroluminescence device employing the same | |
| US7862908B2 (en) | Conjugated compounds containing hydroindoloacridine structural elements, and their use | |
| CN100343359C (en) | Material for organic electroluminescent device and organic electroluminescent device using the same | |
| CN102911211B (en) | Organometallic compound and organic electroluminescent device comprising the same | |
| JP5907289B1 (en) | Material for organic electroluminescence device and use thereof | |
| CN1390841A (en) | Methylene pyrrole metal complex, material for luminating element containing it and luminating element | |
| CN101874021A (en) | Azaindenofluorenedione derivative, material for organic electroluminescent element, and organic electroluminescent element | |
| CN106967060A (en) | Serial carbazole derivates and application | |
| EP1808912B1 (en) | Electron transport compound and organic light emitting device comprising the same | |
| CN101077971A (en) | Organic electroluminescent phosphorescence luminescent material and application thereof | |
| CN112952020B (en) | Organic electroluminescent device and display device comprising same | |
| CN103896990B (en) | organic electroluminescent material and application thereof | |
| TWI659086B (en) | Delayed fluorescence compound and organic electroluminescent device using the same | |
| CN110790796A (en) | Novel organic metal iridium complex, preparation method thereof and organic electroluminescent device containing metal iridium complex | |
| CN1259312C (en) | Compound of substituted benzo heterocyclic by electrophosphorescence and luminous ligand thereof | |
| TWI728594B (en) | Organic metal compound and organic light-emitting device | |
| CN104370968A (en) | Isoquinoline metal complex, and preparation method and application thereof | |
| TWI675037B (en) | Organic metal compound and organic light-emitting device | |
| CN1322094C (en) | Cyclic metallic platinum compounding agent electrofluor scence material containing triaryl amine functional redical | |
| CN1259317C (en) | Derivant of electrophosphorescence 1,8-naphthimide and luminous ligand thereof | |
| CN1803970A (en) | Organic metal complex and organic electro photoluminescence device comprising the same | |
| CN1376758A (en) | Electroluminescent organic material and its application | |
| TWI662043B (en) | Organic metal compound and organic light-emitting device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060614 Termination date: 20100226 |