CN104761550A - Preparation method of bisbenzimidazole group-containing phenanthroline-type derivative and organic light-emitting device (OLED) - Google Patents
Preparation method of bisbenzimidazole group-containing phenanthroline-type derivative and organic light-emitting device (OLED) Download PDFInfo
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- CN104761550A CN104761550A CN201510109803.5A CN201510109803A CN104761550A CN 104761550 A CN104761550 A CN 104761550A CN 201510109803 A CN201510109803 A CN 201510109803A CN 104761550 A CN104761550 A CN 104761550A
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Abstract
The invention provides a bisbenzimidazole group-containing phenanthroline-type organic semiconductor material, which is excellent in thermo-stability, solubility and film-forming property. An optical-spectrum test proves that the maximum light-emitting wavelength of the material is in the range of blue light. Meanwhile, because that the structure of the light-emitting material contains phenanthroline and two bisbenzimidazole groups, the light-emitting material is good in symmetry, excellent in charge transfer capacity and high in glass-transition temperature. In addition, a crystallization effect can be prevented.
Description
Technical field
The present invention relates to organic photoelectrical material field, particularly relate to a class bisbenzimidazole base phenanthroline analog derivative, preparation method and organic luminescent device.
Background technology
Organic electroluminescent (EL) device (hereinafter, simply referred to as " organic EL device ").Generally be made up of two opposed electrodes and at least one deck organic luminescent compounds be inserted between these two electrodes.Electric charge is injected in the organic layer formed between the anode and cathode, to form electronics and hole pair, makes the organic compound with fluorescence or phosphorescent characteristics create light emission.
Along with the development of information age, there is the concern that the organic EL display (OLEDs) of efficient, energy-conservation, lightweight and big area white-light illuminating are more and more subject to people.OLED technology is paid close attention to by the scientist in the whole world, and relevant enterprise and laboratory are all in the research and development carrying out this technology.As a kind of novel LED technology, there is active illuminating, light, thin, good contrast, energy consumption are low, organic electroluminescence device that is that can be made into the features such as flexible device proposes higher requirement to material.
1987, Tang and VanSlyke of Eastman Kodak company of the U.S. reported the breakthrough in organic electroluminescent research.And the application purpose such as total colouring and illumination will be realized, luminescent device must have certain efficiency and life-span.Blue light electroluminescence efficient, stable at present, white light parts are fewer, and the blue light material of high mobility, high thermal stability also compares shortage.
Phenanthroline has the two dimensional structure of rigidity, this type of material is made to have higher electronic mobility, simultaneously due to the rigid structure of itself, contribute to the raising of material thermostability, bisbenzimidazole base phenanthroline analog derivative has become good electron transport material in organic photoelectric equipment, due to the deficiency of synthesis technique, cannot meet industrialized demand, research for this material is only limited to device aspect, seriously hinders the industrialization promotion of material.The structure of bisbenzimidazole base phenanthroline analog derivative early has patent to mention, US20060111388, US20060264414 general structure comprises this structure, but is applied on fluorescent reagent always.Propose duplicate structure in patent CN201010561766.9, but do not propose a more reasonably synthetic method.Structure described in patent TW200934776A is unsymmetric structure.Some pertinent literatures are also had to propose similar structures, but all without corresponding synthetic method.
Summary of the invention
For the deficiency in above-mentioned field, the invention provides a kind of synthetic method of efficient synthesis bisbenzimidazole base phenanthroline analog derivative, the method is easy and simple to handle, productive rate is high, product purity is high, and cost for purification is low, has great meaning to the industrialization promotion of this material.
Bisbenzimidazole base phenanthroline analog derivative molecular structural formula provided by the invention is:
（I）
（II）
The method of efficient synthesis bisbenzimidazole base phenanthroline derivative, comprise the steps: that (1) is with 4 for formula (I) and formula (II), 7-dimethyl-1,10-phenanthroline is raw material, tindioxide is that catalyzer carries out oxidizing reaction, the dialdehyde compounds obtained and adjacent aminodiphenylamine are carried out cyclization reaction, and obtain target compound (I), its reaction scheme is such as formula (a); (2) with 2,9-phenylbenzene-4,7-dimethyl-1,10-phenanthroline is raw material, and tindioxide is that catalyzer carries out oxidizing reaction, and the dialdehyde compounds obtained and adjacent aminodiphenylamine are carried out cyclization reaction, obtain target compound (II), its reaction scheme is such as formula (b).
(a)
(b)
Present invention also offers the preparation method of bisbenzimidazole base phenanthroline analog derivative, it is characterized in that, the synthesis of compound (I) comprises the steps:
Step S1: add raw material, catalysts and solvents in the reaction vessel after degassed;
Step S2: raise temperature of reaction and reflux, fully reacting;
Step S3: washing, cross silica gel funnel, recrystallization, obtains the dialdehyde compounds in formula (a).
Step S4: add raw material, alkali and solvent in the reaction vessel after degassed;
Step S5: raise temperature of reaction and reflux, fully reacting, TLC detection reaction progress;
Step S6: cooling, washing, extraction, separatory, recrystallization;
The synthesis of compound (II) comprises the steps:
Step N1: add raw material, catalysts and solvents in the reaction vessel after degassed;
Step N2: raise temperature of reaction and reflux, fully reacting;
Step N3: washing, cross silica gel funnel, recrystallization, obtains the dialdehyde compounds in formula (a).
Step N4: add raw material, alkali and solvent in the reaction vessel after degassed;
Step N5: raise temperature of reaction and reflux, fully reacting, TLC detection reaction progress;
Step N6: cooling, washing, extraction, separatory, recrystallization;
A kind of described organic luminescent device made containing bisbenzimidazole base phenanthroline analog derivative, it comprises the first electrode, the second electrode and is placed in the one or more organic compound layers between described first electrode, described second electrode, it is characterized in that, organic compound layer described at least one comprises the described compound containing bisbenzimidazole base phenanthroline analog derivative.
Provided by the invention containing bisbenzimidazole base phenanthroline class organic semiconductor material, there is excellent thermostability, there is good solubility and film-forming properties, and by spectrum test, find that the maximum emission wavelength of this material is at blue light range; Simultaneously this luminescent material is due to the existence of phenanthroline in structure and two benzoglyoxaline groups, and material has better symmetry, excellent charge transport ability and high glass-transition temperature and can prevent the effect of crystallization.
embodiment:
The synthesis of described compound (I) comprises the steps:
Described S1 preferably reacts 3-4h at 95 DEG C-105 DEG C;
Described S1 reaction is carried out under nitrogen protection;
Dioxane selected by described S1 solvent: water=96:4;
Described S2 reaction end adopts TLC method to detect;
Described S3 cooling, washing, extraction, separatory, recrystallization;
The synthesis of described compound (II) comprises the steps:
Described N1 temperature of reaction is react 6-10h at 150 DEG C-160 DEG C.
Described N1 reaction is carried out under nitrogen protection;
The selected alkali of described N1 reaction is Sodium Pyrosulfite;
N7 temperature of reaction-78 DEG C described in DMF selected by described N1 solvent.
Described N2 reaction end adopts TLC method to detect;
Described N3 cooling, washing, extraction, separatory, recrystallization;
Compound (I) synthesizes example:
20.8g(0.1mol is added in 5L there-necked flask) 4,7-dimethyl-1,10-phenanthrolines, 49.9g (0.45mol) tin anhydride, joins the mixing solutions of 1300ml dioxane and 55ml water, and temperature is elevated to 100 DEG C, back flow reaction 3-4 hour, reaction terminates to adopt TLC method to determine, stopped reaction crosses diatomite funnel while hot, solid is had to separate out after cooling, tetrahydrofuran (THF) recrystallization, obtains twain-aldehyde compound compound light yellow crystal 19.1g (0.081mol), yield 81%.
By 19g(0.08mol in 1L there-necked flask) above-mentioned dialdehyde compounds, 36.6g(0.2mol) adjacent aminodiphenylamine, 38g(0.2mol) Sodium Pyrosulfite is placed in 400mlDMF, backflow reaction overnight, after TLC detection reaction terminates, is cooled to room temperature, washing, extraction into ethyl acetate, obtains 33.9g(0.06mol through recrystallization) white solid, yield 75%.
Compound (II) synthesizes example:
36g(0.1mol is added in 5L there-necked flask) 2,9-phenylbenzene-4,7-dimethyl-1,10-phenanthroline, 49.9g (0.45mol) tin anhydride, join the mixing solutions of 1300ml dioxane and 55ml water, temperature is elevated to 100 DEG C, back flow reaction 3-4 hour, and reaction terminates to adopt TLC method to determine, stopped reaction, cross diatomite funnel while hot, after cooling, have solid to separate out, tetrahydrofuran (THF) recrystallization, obtain twain-aldehyde compound compound light yellow crystal 31g (0.08mol), yield 80%.
By 27.2g(0.07mol in 1L there-necked flask) above-mentioned dialdehyde compounds, 33g(0.18mol) adjacent aminodiphenylamine, 34.2g(0.18mol) Sodium Pyrosulfite is placed in 350mlDMF, backflow reaction overnight, after TLC detection reaction terminates, is cooled to room temperature, washing, extraction into ethyl acetate, obtains 39.5g(0.055mol through recrystallization) white solid, yield 78.6%.
By fast atom bombardment mass spectroscopy(FABMS) (FABMS) method, carry out the ultimate analysis of compound.The results are shown in Table 1, and wherein MS/FAB (M+) is the molecular weight recorded by FABMS:
Table 1
The above embodiment only have expressed embodiments of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Comparative example
Using the compound of chemical formula a as light emitting host material, the compound of chemical formula b is as dopant material, the 2-TNATA (4 that chemical formula c represents, 4,4-tri-(N-naphthyl)-N-phenyl amino)-triphenylamine) as hole-injecting material, α-NPD (the N that chemical formula d represents, N '-two (naphthyl)-N, N '-diphenylbenzidine) as hole mobile material, make the organic luminescent device of structure below: ITO/2-TNATA (80nm)/α-NPD (30nm)/compound a+compound b (30nm, wherein b content is 8%)/Al q
3(30nm)/LiF (0.5nm)/Al (60nm).Wherein, Alq
3oxine aluminium.
Chemical formula a chemical formula b
Chemical formula c chemical formula d
Corning(is healthy and free from worry) society 15 Ω/cm2 (1000) ITO glass substrate is cut into the size of 50mm*50mm*0.7mm.Subsequently in microwave, successively at acetone, Virahol, cleans 15 minutes in pure water respectively, in ultraviolet, clean 30 minutes again.At the 2-TNATA of thereon vacuum evaporation 80 nm thickness, form hole injection layer.Above hole injection layer, the α-NPD of vacuum evaporation 30 nm thickness, defines hole transporting layer.The compound that above hole transporting layer, the chemical formula a of vacuum evaporation 30nm thickness represents and the compound that chemical formula b represents (doping rate 8%), define luminescent layer.The Alq of vacuum evaporation 30 nm thickness above luminescent layer
3, define electron supplying layer.Vacuum evaporation LiF 0.5nm (electron injection) and Al 60nm successively above electron supplying layer, has made organic luminescent device.In this comparing embodiment 1 and following Application Example 1-24, the EL evaporator adopting DOV company to manufacture carries out vacuum evaporation.
Application Example:
Adopt as the method in comparative example 1, make the organic luminescent device with structure below, difference is as luminescent layer compound, that replace compound a to adopt is the compound represented in preparation example: ITO/2-TNATA (80nm)/α-NPD (30nm)/formula (I) or formula (II)+compound b] (25nm, wherein b content is 8.0%)/Alq
3(30nm) organic luminescent device of the structure of/LiF (0.5nm)/Al (60nm).
Measure embodiment 1: the luminescent properties of formula (I), formula (II) compound and comparative sample
Under similarity condition, measure the sample of the sample of comparing embodiment 1 and Application Example formula (I), formula (II).Measure and adopt KEITHLEY Keithley 235 type source measuring unit,
spectrascanPR650spectral scan colourimeter, to evaluate driving voltage, luminosity, luminous efficiency, glow color.The results are shown in Table 2:
Table 2
Represented by table 2, above-mentioned sample shows glow color for blue in 460-480nm wavelength region.The sample of Application Example compares with the sample of comparing embodiment 1, uses the organic luminescent device of the organic layer of bisbenzimidazole base phenanthroline derivative can have the efficiency of lower driving voltage, higher brightness and Geng Gao.
Although the present invention's exemplary embodiment has carried out special description, but should be appreciated that those of ordinary skill in the art can carry out the change in various forms and details to it when not departing from the spirit of the present invention and scope that following patent requirement limits.
Claims (9)
1. bisbenzimidazole base phenanthroline analog derivative molecular structural formula provided by the invention is:
（1）
（II）。
2. the preparation method of bisbenzimidazole base phenanthroline analog derivative formula (I) according to claim 1, is characterized in that, comprise the steps:
Step S4: add raw material (twain-aldehyde compound compound), alkali and solvent in the reaction vessel after degassed;
Step S5: raise temperature of reaction and reflux, fully reacting, TLC detection reaction progress;
Step S6: cooling, washing, extraction, separatory, chromatography column is separated.
3. preparation method according to claim 2, is characterized in that, raw material (twain-aldehyde compound compound) in described step S4 is by 4,7-dimethyl-1,10-phenanthroline, tin anhydride catalyzed oxidation.
4. preparation method according to claim 3, is characterized in that, comprises the steps:
Step S1: add raw material, catalysts and solvents in the reaction vessel after degassed;
Step S2: raise temperature of reaction and reflux, fully reacting;
Step S3: washing, cross silica gel funnel, recrystallization, obtains dialdehyde compounds.
5. the preparation method of bisbenzimidazole base phenanthroline analog derivative formula (II) according to claim 1, is characterized in that, comprise the steps:
Step N4: add raw material (twain-aldehyde compound compound), alkali and solvent in the reaction vessel after degassed;
Step N5: raise temperature of reaction and reflux, fully reacting, TLC detection reaction progress;
Step N6: cooling, washing, extraction, separatory, recrystallization.
6. preparation method according to claim 5, is characterized in that, raw material (twain-aldehyde compound compound) in described step S1 is by 2,9-phenylbenzene-4,7-dimethyl-1,10-phenanthroline, tin anhydride catalyzed oxidation.
7. preparation method according to claim 6, is characterized in that, comprises the steps:
Step N1: add raw material, catalysts and solvents in the reaction vessel after degassed;
Step N2: raise temperature of reaction and reflux, fully reacting;
Step N3: washing, cross silica gel funnel, recrystallization, obtains dialdehyde compounds.
8. described in one kind, contain the organic luminescent device that bisbenzimidazole base phenanthroline analog derivative is made, it comprises the first electrode, the second electrode and is placed in the one or more organic compound layers between described first electrode, described second electrode, it is characterized in that, organic compound layer described at least one comprises the described compound containing bisbenzimidazole base phenanthroline analog derivative.
9. a class bisbenzimidazole base phenanthroline analog derivative provided by the invention, preparation method and the application in organic electroluminescence device thereof.This bisbenzimidazole base phenanthroline analog derivative has high luminous efficiency, high luminous efficiency shows that this compound can be used as luminescent material or light emitting host material, especially can as material of main part, for showing high-level efficiency, high brightness, long lifetime in organic electroluminescence device, there is the advantage that manufacturing cost is lower, reduce the manufacturing cost of organic electroluminescence device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004270A (en) * | 2019-12-27 | 2020-04-14 | 厦门天马微电子有限公司 | Organic compound, electron transport material and application thereof |
Citations (3)
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|---|---|---|---|---|
| US4772563A (en) * | 1984-08-13 | 1988-09-20 | Hsc Research Development Corporation | 1,10-phenanthroline derivatives and use in fluorescence immunoassays |
| CN102127073A (en) * | 2010-11-26 | 2011-07-20 | 深圳大学 | Star-shaped compound taking phenanthroline as core and luminescent device comprising same |
| CN103468247A (en) * | 2013-09-18 | 2013-12-25 | 贵州大学 | Molecular tweezer type phenanthroline-benzoxazole fluorescent reagent, as well as preparation method and application thereof |
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2015
- 2015-03-13 CN CN201510109803.5A patent/CN104761550A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4772563A (en) * | 1984-08-13 | 1988-09-20 | Hsc Research Development Corporation | 1,10-phenanthroline derivatives and use in fluorescence immunoassays |
| CN102127073A (en) * | 2010-11-26 | 2011-07-20 | 深圳大学 | Star-shaped compound taking phenanthroline as core and luminescent device comprising same |
| CN103468247A (en) * | 2013-09-18 | 2013-12-25 | 贵州大学 | Molecular tweezer type phenanthroline-benzoxazole fluorescent reagent, as well as preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| HYUNJU OH等: "Synthesis of heteroleptic Ru(II) complexes ligated with 1,3-dihydro-1,1,3,3-tetramethyl-7,8-diazacyclopenta[1]phenanthren-2-one", 《SYNTHETIC METALS》 * |
| 李炎等: "苯并咪唑及其衍生物合成与应用研究进展", 《有机化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004270A (en) * | 2019-12-27 | 2020-04-14 | 厦门天马微电子有限公司 | Organic compound, electron transport material and application thereof |
| CN111004270B (en) * | 2019-12-27 | 2023-10-20 | 厦门天马微电子有限公司 | Organic compound, electron transport material and application thereof |
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Application publication date: 20150708 |