CN104230645A - Blue light-emitting material - Google Patents
Blue light-emitting material Download PDFInfo
- Publication number
- CN104230645A CN104230645A CN201410434464.3A CN201410434464A CN104230645A CN 104230645 A CN104230645 A CN 104230645A CN 201410434464 A CN201410434464 A CN 201410434464A CN 104230645 A CN104230645 A CN 104230645A
- Authority
- CN
- China
- Prior art keywords
- substituted
- phenanthryl
- compound
- naphthyl
- replaces
- 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.)
- Pending
Links
- IQSUNBLELDRPEY-UHFFFAOYSA-N CCC1=CC=CC1 Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention discloses a blue organic semiconductor (I) as shown in the specification. A benzophenanthrene derivative is taken as a main core, and electron holes and electronic condensed aromatic heterocycle are connected in a chemical bonding manner. The material is excellent in thermal resistance and light emitting property with high efficiency and a long service life, and a dark blue organic light emitting device with a long service life is obtained when the material is used in a light-emitting layer of an organic light-emitting diode.
Description
Technical field
The present invention relates to luminous organic material and the application at organic luminescent device thereof, especially a kind of blue organic semiconductor material, can be applicable to organic light emission OLED, improves device performance.
Background technology
Organic semiconductor material belongs to novel optoelectronic materials, and its broad scale research originates from 1977 by Hideki Shirakawa, and A. Heeger and A. McDiamid has found that electric conductivity can reach the doped polyacetylene of copper level jointly.Subsequently, the C. Tang etc. of KodaK company in 1987 has invented organic molecule photodiode (OLED), with nineteen ninety Cambridge University R. Friend and A. Holmes invented polymer LED P-OLED, and S. Forrest in 1998 and M. Thomson have invented the higher Phosphorescent LED P HOLED of efficiency.Due to organic semiconductor material have structure easily adjust can obtain numerous in variety, can be with adjustable, low cost benefit even as plastics film processing, add that organic semiconductor is at conductive film, xerox, photovoltaic solar cell is applied, OTFT logical circuit, with numerous application such as organic light emission OLED flat pannel display and illumination, Bai Chuan-Heeger-McDiamid three scientists obtained Nobel chemistry Prize in 2000.
As the Organic Light Emitting Diode of flat panel display of future generation, organic photoelectric semi-conductor requires: 1. high-luminous-efficiency; 2. excellent electronics and hole stability; 3. suitable glow color; 4. excellent film forming processibility.In principle, major part conjugacy organic molecule (comprising star beam), conjugacy polymkeric substance, have with the organic heavy metal complex compound containing conjugacy chromophoric group part and possess electroluminescence performance, be applied in all kinds of photodiode, as organic molecule photodiode (OLED), polymer organic LED (POLED), Phosphorescent photodiode (PHOLED).The phosphorescence PHOLED dual-purpose luminescence mechanism of singlet excited state (fluorescence) and Triplet Excited State (phosphorescence), obviously much higher than small molecules OLED and polymer POLED luminous efficiency.PHOLED manufacturing technology and outstanding PHOLED material be all realize low power consumption OLED display and lighting institute requisite.The quantum yield of PHOLED and luminous efficiency are 3-4 times of fluorescence OLED material, therefore decrease the heat of generation, increase the competitive power of OLED display panel.This point provides and makes OLED display or illumination generally surmount the possibility of LCD display and conventional light source.Thus, phosphorescent OLED material has been mixed more or less in existing high-end OLED full-color display device.
Phosphorescent OLED material is as bidentate chelating ligand by the organic light emission group containing certain conjugacy, ring metal-ligand complex compound is formed with metallic element, high energy light according under under (as ultraviolet excitation) or charge injection (being electrically excited) condition, because ring metal-ligand charge transfer (MLCT) becomes exciton, be then returned to ground state and cause luminescence.In OLED, the injection of electric charge is by after anode applies positive voltage, from anode injected hole, negative electrode injects electronics after applying negative voltage, respectively through electron transfer layer and transporting holes layer, enter in the bulk material of emission layer simultaneously, electronics finally enters the minimum last occupied molecular orbital (LUMO) in light-emitting dopant, and hole enters the highest occupied molecular orbital(HOMO) (HOMO) in light-emitting dopant and forms excited state luminescent dopant agent molecule (exciton state).Along with launching luminous energy after exciton state is returned to ground state, it launches the energy gap (HOMO-LUMO energy level difference) that luminous energy wavelength just correspond to light emitting molecule doping agent.
The heavy metal organic ligand complex compound of existing many reports, enhances electron spinning rail effect by the impact of heavy metal, make to become very strong and present excellent phosphorescent emissions by more weak phosphorescence.Three (phenylpyridine) iridium (III) of such as green light coordinates complex compound, referred to as Ir (ppy)
3, having structural formula is:;
Ir(ppy)
3；
The FirPic launching blue light has following structural formula:
FirPic；
Main part 4,6-phenyl-difluoride yl pyridines wherein dominates glow color;
Three (octyl quinoline) iridium (III) of red-emitting coordinates complex compound, has excellent efficient transmission performance (Adv. Mater.19,739(2007)) its structural formula is:
Ir(piq-hex)
3。
Luminescent layer generally mixes one by a small amount of luminescent material to be had in the semiconductor body material of more high level and forms.Compared to ruddiness and the green glow of comparative maturity, the efficiency of Nan dian Yao and purity of color (<0.15) are also difficult to reach requirement simultaneously.Study mechanism finds, along with triplet raises, not only the speed of radiative transition becomes large, also along with the increase of nonradiative transition speed, and the increase amplitude of often the latter is more obvious, total action effect makes luminous efficiency decline on the contrary, and during this just causes blue light emitting material to be studied, the blue shift of emission wavelength and high-level efficiency are difficult to realize simultaneously, often turn round and look at this thin that.Compared to blue phosphor materials, fluorescent blue luminescent material has the longer life-span, and cost is lower.Current business-like blue light material is mainly based on fluorescent material.But fluorescent material luminous efficiency is low, how to raise the efficiency and ensure that purity of color is the study hotspot of recent years always.Document (J. Mater. Chem., 2009,19,1865 – 1871) report a kind of phenanthro-imidazoles blue light material TPIP connected based on symmetry, colour code is (0.15,0.10), but due to single electronegativity reason, external quantum efficiency is less than 6%, and CIE does not also reach display requirement.Recently, document (Sci. Technol. Adv. Mater. 15 (2014) 034201 (7pp)) reports the luminous efficiency increasing blue light material by one deck EEL efficiency promoting layer and TTF phenomenon, the EQE obtained is up to 11.5%, and there is good CIE chromaticity coordinates (0.138,, but have no concrete detailed structural information report 0.092).
Therefore, for meeting the various requirement that industrial production constantly promotes, obtain efficient, long-life organic OLED display and illuminating product, organic blue light emitting material that exploitation is better, efficiency is higher is imperative.
Simple benzophenanthrene is that the compound of core existing to disclose CN201210175578.1 such as () Wang Hui:
wherein R to be carbonatoms be 6 ~ 50 connection unit, but its preparation or performance not good.
Summary of the invention
The present invention disclose a kind of based on triphenylene as the Organic Electricity of kernel to luminescent material, have good hole and electric transmission and luminescent properties concurrently, heat-resistant stability and excellent electrochemical stability, described illuminant compound has following general structure:
（Ⅰ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the R in described compound
1-2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
Scope according to this patent, compound has formula II structure in one case:
（Ⅱ）
Scope according to this patent, compound described in another case has (III) structure:
（Ⅲ）
No matter be general formula (II) or general formula (III), it is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
Ar in described compound
3 ~ 4for same or different following groups, be preferably:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, substituted-phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
Without prejudice under scope of the present invention, described compound has the structure of (IV) as follows:
Wherein R
1-2for H, D, F, the alkyl that carbonatoms number is less than 8, the alkoxyl group that carbonatoms is less than 8, phenyl, substituted-phenyl, fragrant heterocycle or replacement virtue heterocycle;-N (Ar
3-Ar
6)
2preferred structure be:
Ar in described compound
7for phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replace pyrenyl, phenanthryl, replace phenanthryl, anthryl, replace anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base.For being adjusted to mazarine (PL<465 nm), X in benzo virtue heterocycle is selected to be electrically connected unit for inhaling, as SO2, Si (R)
2be helpful, be conducive to HOMO(highest occupied molecular orbital) improve, increase energy gap.
Especially according to content of the present invention, it is characterized in that the preferred compound structure included but not limited to has following preferred structure:
。
What is more important of the present invention is that described organic semiconductor is applied to organic luminescent device.Usually, the simplest Organic Light Emitting Diode of the present invention is made up of following a few part:
(a) negative electrode
(b) anode
The sandwich organic semiconductor luminescent layer between negative electrode and positive electrode of (c), this luminescent layer comprises a material of main part and a phosphor dopant;
The sandwich organic semiconductor blue light emitting material between anode and luminescent layer of (d), it is characterized in that described organic semiconductor hole transport layer directly contacts compound (I) with luminescent layer and formed, its thickness is 5-100nm, has following general structure:
（Ⅰ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, phenanthryl, pyrenyl, thienyl;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, naphthyl, anthryl;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.; Compound according to claim 1, is characterized in that described compound has formula II structure:
（Ⅱ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, phenyl, naphthyl, phenanthryl, pyrenyl, thienyl;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, naphthyl, anthryl;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
Organic compound according to application claims, is characterized in that described compound has formula (III) structure:
（Ⅲ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, phenyl, naphthyl, phenanthryl, pyrenyl, thienyl;
It is characterized in that the R1 in described compound
~2 are less than the alkyl of 12, the alkoxyl group that carbonatoms is less than 12, phenyl, naphthyl, anthryl for carbonatoms;
It is characterized in that the Ar3 in described compound
~4 is same or different following groups:
Wherein, R
3 ~ 5for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
，
Ar
1-6for phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replace pyrenyl, phenanthryl, replace phenanthryl, anthryl, replace anthryl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base.Wherein Ar
7-8for H, D, F, naphthyl, the alkyl that carbon atom is less than 12, benzophenanthrene, pyrene, thienyl, substituted thiophene base, carbazyl, substituted carbazole base.
In traditional Organic Light Emitting Diode chip (Fig. 1), normally adopt transparent conducting glass 101, or be coated with evaporation one deck hole injection layer HIL(102 on indium-tin-oxide ITO), then one deck hole transmission layer HTL(103 successively), luminescent layer EML(104), electron transfer layer ETL(105), electron injecting layer EIL(106), finally add layer of metal (107), as aluminum metal layer, as anode conducting and sealing ply.When ITO connects positive electricity, after aluminium connects negative electricity to certain electric field, hole transfers to EML from ITO through HIL injection and HTL, and the EIL that electronics connects from aluminium inject after, transfer to EML. electronics and hole is met at EML, is combined into exciton (Exciton) through ETL, then part exciton gives off energy with optical radiation form and gets back to ground state.The wavelength of optical radiation is determined by the energy gap of the light-emitting dopant in EML layer.
Organic semiconductor according to this patent, because its emission wavelength is in 400-480 nm scope, is applicable to being applied to the luminescent layer in organic blue light emitting diode.In an organic light emitting device, more stable with electric field change (brightness regulation) for making luminous efficiency and color obtain, usual EML by a bandwidth larger as material of main part, less the forming as light-emitting dopant of energy gap.In EML, dopant content can be 1-49%(weight), preferably general at 1-10%.
Do not departing from scope of the invention situation, other organic host material is also applicable to the present invention, and the compound described in general formula (I) is as light-emitting dopant, it is characterized in that having the compound described in formula I containing blue light doping agent in luminescent layer, emission wavelength is 430-480nm.
Do not departing from scope of the invention situation, the compound described in general formula (I) can be used as luminescent layer material of main part, can mix as other luminescent material in luminescent layer, or light-emitting dopant of the present invention, forms luminescent layer.Material of main part weight content is generally at 50%-99%, and luminescent dopant agent content is generally at weight content 1-49%.
For obtaining efficient green glow and ruddiness OLED, typically use triplet state phosphorescent OLED, emission layer wherein contains phosphorescent light-emitting materials, as Ir (ppy)
3for green glow, or Ir (Piq)
3as red dopant, with concentration luminescence (weight) material of 2 to 15%, be doped in a material of main part,
Ir(ppy)
3 ，
Ir(Piq）
3 ，
What material of main part was conventional is that a kind of material of main part is 4,4 '-N, N '-two carbazole-biphenyl (CBP) containing carbazole or arylamine Structure type material:
。
For reaching excellent phosphorescent devices performance, on anode, can an optional hole injection layer, as blue or green in phthalein blue (CuPc) or other compounds containing fragrant ammonia (Appl.Phys.Lett., 69,2160 (1996), as m-TDATA,
。
Similarly, between hole injection layer and emission layer EML, often to select a hole transmission layer, more often use 4,4 '-bis-[N-(1-naphthyl)-N-phenylamino] biphenyl (α-NPD)
。
For the injection in balance electronic and hole, improve luminous efficiency, can optional electric transmission hole barrier (ETHB) material, example is 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene TPBi, and its structure is:
。
Between ETHL and negative electrode, also usually use electron injecting layer.The electron injecting layer metal Lithium that normally work content is lower, or its compound is as 8-hydroxyl Lithium (Liq):
。
Therefore, Fig. 1 one typically constructs, but is not unique application structure.In traditional Organic Light Emitting Diode chip (Fig. 1), normally adopt transparent conducting glass 101, or be coated with evaporation one deck hole injection layer HIL(102 on indium-tin-oxide ITO), then one deck hole transmission layer HTL(103 successively), luminescent layer EML(104), electron transfer layer ETL(105), electron injecting layer EIL(106), finally add layer of metal (107), as aluminum metal layer, as anode conducting and sealing ply.When ITO connects positive electricity, after aluminium connects negative electricity to certain electric field, hole transfers to EML from ITO through HIL injection and HTL, and the EIL that electronics connects from aluminium inject after, transfer to EML. electronics and hole is met at EML, is combined into exciton (Exciton) through ETL, then part exciton gives off energy with optical radiation form and gets back to ground state.The wavelength of optical radiation is determined by the energy gap of the light-emitting dopant in EML layer.
Organic semiconductor according to this patent, because its emission wavelength is in 410-480 nm scope, is applicable to being applied to the luminescent layer in organic blue light emitting diode.In an organic light emitting device, more stable with electric field change (brightness regulation) for making luminous efficiency and color obtain, usual EML by a bandwidth larger as material of main part, less the forming as light-emitting dopant of energy gap.In EML, dopant content can be 1-49%(weight), preferably general at 1-10%.Known typical Blue-light emitting host material has ABPN:
。
Do not departing from scope of the invention situation, other organic host material is also applicable to the present invention, and the compound described in general formula (I) is as light-emitting dopant or material of main part, it is characterized in that having the compound described in formula I containing blue light doping agent in luminescent layer, emission wavelength is 440-480nm.Wherein the general thickness of organic semiconductor layer is 50-250nm, and preferred total thickness is 80-180nm.
The invention has the beneficial effects as follows, this material has excellent thermotolerance and the characteristics of luminescence of efficient and long life, is applied to the luminescent layer of Organic Light Emitting Diode, obtains navy blue long-life organic luminescent device.
Accompanying drawing explanation
Fig. 1 organic LED structure schematic diagram.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail the specific embodiment of the present invention below in conjunction with examples of implementation.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar popularization when intension of the present invention.Therefore the present invention is not by the restriction of following public specific embodiment.
embodiment 1.the synthesis of compound 10:
。
the synthesis of intermediate 3,6-bis-boron ester-5,8-phenylbenzene benzophenanthrene:in the 100 mL three-necked bottles with thermometer and prolong, add bromo-5, the 8-phenylbenzene benzophenanthrene 2.15g(4mmol of 3,6-bis-successively),
connection boric acid pinacol ester2.54g(10 mmol), tribenzal acetone two palladium 0. 2g(0.2 mmol), S-phos 0.25g(0.6mmol) and, Potassium ethanoate 1.17g(12 mmol), toluene 20ml, nitrogen replacement, is warming up to back flow reaction 16h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 1.58g(65%), MS=612.
the synthesis of final product:in the 100 mL three-necked bottles with thermometer and prolong, add 3,6-bis-boron ester-5,8-phenylbenzene benzophenanthrene 2.00g(3.16mmol successively),
the bromo-10-of 9-(2-naphthyl) anthracene2.42g(6.32 mmol), Pd (PPh
3)
40. 2g(0.16 mmol), salt of wormwood 1.75g(12.64 mmol), toluene 30ml, ethanol 15ml, H
2o 10ml, nitrogen replacement, is warming up to back flow reaction 16h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=10:1, receives solid 1.87g(65%), MS=985, PL(THF): <475nm (blue light).
embodiment 2.the synthesis of compound 21:
。
the synthesis of intermediate M1:in the 250 mL three-necked bottles with thermometer and prolong, add 3,6-dibromo phenanthrenequione 6.94g(18.96mmol successively), dibenzyl ketone 4.18g(19.9 mmol), KOH 1.78g(30.48mmol) and, methyl alcohol 120ml, is warming up to back flow reaction 2h.TLC point board monitoring reaction is to completely.Be cooled to room temperature, filter, by filter residue methanol wash, filter and obtain required product, receive brown solid 6.4g(62.5%); Need not purify and be directly used in next step reaction.
the synthesis of intermediate M2:in the 100 mL three-necked bottles with thermometer and prolong, add M1 4.5g(8.325mmol successively), trimethylsilyl acetylene 1.8g(18.3 mmol), o-Xylol 45ml, is warming up to back flow reaction 12h.Be cooled to room temperature, filter, by filtrate by the anti-phase precipitation of methyl alcohol, filter, short column of silica gel, the pure hexane of moving phase, receives white solid 1.9g(36.7%).
the synthesis of intermediate M3:with in 50 mL two neck bottles of thermometer, add M2 1.9g(3.11mmol successively), tetrabutyl ammonium fluoride 0.9g(3.42 mmol), THF20ml, room temperature reaction 4h.By filtrate by the anti-phase precipitation of methyl alcohol, filter, receive white solid 1.3g(78%).
the synthesis of intermediate M4:in the 100 mL three-necked bottles with thermometer and prolong, add cumidine 14.8g(109mmol successively), 4-bromine diphenylene-oxide 18g(72.87 mmol), tribenzal acetone two palladium 1g(1.09 mmol), BINAP1.35g(21.8mmol), sodium tert-butoxide 13.9g(145 mmol), toluene 180ml, nitrogen replacement, is warming up to back flow reaction 3h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 18g(81.8%).
the synthesis of final product M5:in the 100 mL three-necked bottles with thermometer and prolong, add M4 0.36g(1.2mmol successively), M3 0.269g(0.5 mmol), tribenzal acetone two palladium 0.02g(0.025 mmol), S-phos 0.04g(0.1mmol), sodium tert-butoxide 0.192g(2 mmol), toluene 15ml, nitrogen replacement, is warming up to back flow reaction 3h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 0.4g(81.6%), MS=979, PL(THF): <475nm (blue light).
embodiment 3.the synthesis of compound 22:
。
the synthesis of intermediate M6:in the 100 mL three-necked bottles with thermometer and prolong, add cumidine 14.8g(109mmol successively), 4-bromine dibenzothiophene 19.2g(72.87 mmol), tribenzal acetone two palladium 1g(1.09 mmol), BINAP1.35g(21.8mmol), sodium tert-butoxide 13.9g(145 mmol), toluene 180ml, nitrogen replacement, is warming up to back flow reaction 3h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 18.9g(79%).
the synthesis of final product:in the 100 mL three-necked bottles with thermometer and prolong, add M6 0.66g(2.1mmol successively), M3 0.538g(1 mmol), tribenzal acetone two palladium 0.048g(0.05 mmol), P (t-Bu) 3 0.16g(0.2mmol), sodium tert-butoxide 0.38g(4 mmol), toluene 25ml, nitrogen replacement, is warming up to back flow reaction 16h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 0.8g(79.2%), MS=1010, PL(THF): <475nm (blue light).
embodiment 4.the synthesis of compound 24:
。
the synthesis of intermediate M8:with in 250 mL three-necked bottles of thermometer, add phenanthrenequione 10.0g(48mmol successively), NBS 18g(109 mmol), vitriol oil 80ml, room temperature reaction 3h.Pour in frozen water, receive brown-red solid, DMSO recrystallization obtains product 16g(45%).
the synthesis of intermediate M9:in the 250 mL three-necked bottles with thermometer and prolong, add 2,7-dibromo phenanthrenequione 6.94g(18.96mmol successively), dibenzyl ketone 4.18g(19.9 mmol), KOH 1.78g(30.48mmol) and, methyl alcohol 120ml, is warming up to back flow reaction 2h.TLC point board monitoring reaction is to completely.Be cooled to room temperature, filter, by filter residue methanol wash, filter and obtain required product, receive brown solid 8.86g(86.5%); Need not purify and be directly used in next step reaction.
the synthesis of intermediate M10:in the 100 mL three-necked bottles with thermometer and prolong, add M9 8.68g(16.4mmol successively), trimethylsilyl acetylene 3.6g(18.3 mmol), o-Xylol 90ml, is warming up to back flow reaction 12h.Be cooled to room temperature, filter, by filtrate by the anti-phase precipitation of methyl alcohol, filter, short column of silica gel, the pure hexane of moving phase, receives white solid 1.83g(18.5%).
the synthesis of intermediate M11:with in 50 mL two neck bottles of thermometer, add M10 1.83g(3mmol successively), trifluoroacetic acid 0.41g(3.6 mmol), trifluoroacetic acid and each 20ml of THF, back flow reaction 4h.By filtrate by the anti-phase precipitation of methyl alcohol, filter, receive white solid 1.3g(78%).
the synthesis of final product:in the 100 mL three-necked bottles with thermometer and prolong, add M4 0.47g(1.58mmol successively), M11 0.40g(0.75 mmol), tribenzal acetone two palladium 0.03g(0.0375 mmol), P (t-Bu) 3 0.04g(0.15mmol), sodium tert-butoxide 0.288g(3 mmol), toluene 15ml, nitrogen replacement, is warming up to back flow reaction 16h.Be cooled to room temperature, filter, by filtrate collection, short column of silica gel, the pure hexane of moving phase: methylene dichloride=4:1, receives white solid 0.65g(89.4%), MS=979, PL(THF) <475nm (blue light).
embodiment 5.device application example:
(Nan dian Yao is prepared and is compared): reach 10 at a base vacuum
-5in the Multisource evaporation OLED Preparation equipment of handkerchief, adopt following device mechanism: ITO/m-TDATA(100)/NPD (400)/Host:5% blue light doping agent 6%(300)/TPBi(300)/LiF(10)/Al, use different Host OLED luminescent devices to compare.Wherein the vacuum moulding machine speed of each organic layer and electrode lists in table 1 in the time.
Table 1:OLED device preparation condition (wt concentration 9% of adulterating in luminescent layer).
Table 2:OLED device performance.
Table 2 illustrates that the compounds of this invention 28 is that the blue light doping illuminating OLED of example has obvious dark blue luminescent properties, y value reaches≤and 0.08.Contrast also shows as main body green glow phosphorescent OLED, and compound 10 of the present invention has higher luminous efficiency LE than existing material of main part CBP, and driving voltage is lower.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Any those of ordinary skill in the art, are not departing under technical solution of the present invention ambit, the technology contents of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the protection domain of technical solution of the present invention.
Claims (10)
1. an organic compound, has following general formula:
（Ⅰ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
2. compound according to claim 1, is characterized in that described compound has formula II structure:
（Ⅱ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
3. compound according to claim 1, is characterized in that described compound has formula (III) structure:
（Ⅲ）
It is characterized in that the Ar in described compound
1 ~ 2for H, F, D, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the R in described compound
1 ~ 2for the alkyl that carbonatoms is less than 12, the alkoxyl group that carbonatoms is less than 12, phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replaces pyrenyl, phenanthryl, replaces phenanthryl, anthryl, replaces anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base;
It is characterized in that the Ar in described compound
3 ~ 4following group for same or different:
Wherein, R
3 ~ 6for the alkyl that carbonatoms is less than 12, phenyl, pyridyl; Ar
5 ~ 8for phenyl, naphthyl, substituted naphthyl, phenanthryl, replace phenanthryl etc.
4. according to the compound one of described in claim 1 ~ 3, it is characterized in that triphenylene in described compound with containing C
10-C
20electronegativity fused aromatic rings is connected, and preferred structure is:
。
5., according to the compound one of claim 1 ~ 3 Suo Shu, it is characterized in that triphenylene Ar in described compound
1-Ar
4in at least containing a cavity type arylamine ,-N (Ar
3-Ar
6)
2, preferred structure is:
；
It is characterized in that the Ar in described compound
7for phenyl, substituted-phenyl, naphthyl, substituted naphthyl, pyrenyl, replace pyrenyl, phenanthryl, replace phenanthryl, anthryl, replace anthryl, pyridyl, substituted pyridinyl, thienyl, substituted thiophene base, carbazyl, substituted carbazole base, preferred structure is:
。
6., according to the compound one of claim 1 ~ 3 Suo Shu, it is characterized in that in described compound, triphenylene is connected with electronegativity fused aromatic rings and hole transport ability arylamine simultaneously, preferred structure is:
。
7. an Organic Light Emitting Diode, is characterized in that described Organic Light Emitting Diode is made up of such as lower part:
(a) negative electrode;
(b) anode;
C the sandwich organic semiconductor luminescent layer between negative electrode and anode of (), containing compound according to claim 1 in this luminescent layer.
8. Organic Light Emitting Diode according to claim 7, is characterized in that the light-emitting dopant (weight percent <50%) in described luminescent layer is compound described in claim 1, is preferably compound described in claim 3.
9. Organic Light Emitting Diode according to claim 7, is characterized in that the light-emitting dopant (weight percent <50%) in described luminescent layer is compound described in claim 1, is preferably compound described in claim 5 or 6.
10. Organic Light Emitting Diode according to claim 7, is characterized in that containing a kind of compound in described organic luminous layer, has main body and luminescent dopant function concurrently, be preferably compound described in claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410434464.3A CN104230645A (en) | 2014-08-29 | 2014-08-29 | Blue light-emitting material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410434464.3A CN104230645A (en) | 2014-08-29 | 2014-08-29 | Blue light-emitting material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104230645A true CN104230645A (en) | 2014-12-24 |
Family
ID=52219662
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410434464.3A Pending CN104230645A (en) | 2014-08-29 | 2014-08-29 | Blue light-emitting material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104230645A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557440A (en) * | 2015-02-05 | 2015-04-29 | 江西冠能光电材料有限公司 | Substituted benzophenanthrene derivative organic light emitting diode material |
| WO2017209297A1 (en) * | 2016-06-02 | 2017-12-07 | 国立大学法人名古屋大学 | Triarylene compound and method for producing same |
| WO2023085877A1 (en) * | 2021-11-15 | 2023-05-19 | 주식회사 엘지화학 | Compound and organic light-emitting element comprising same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070102243A (en) * | 2006-04-14 | 2007-10-18 | 주식회사 이엘엠 | Triphenylene derivative and organic light emitting diode using the same |
| KR20100021855A (en) * | 2008-08-18 | 2010-02-26 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
| CN101805266A (en) * | 2008-10-13 | 2010-08-18 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| KR20110054225A (en) * | 2009-11-17 | 2011-05-25 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
-
2014
- 2014-08-29 CN CN201410434464.3A patent/CN104230645A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070102243A (en) * | 2006-04-14 | 2007-10-18 | 주식회사 이엘엠 | Triphenylene derivative and organic light emitting diode using the same |
| KR20100021855A (en) * | 2008-08-18 | 2010-02-26 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
| CN101805266A (en) * | 2008-10-13 | 2010-08-18 | 葛来西雅帝史派有限公司 | Novel organic electroluminescent compounds and organic electroluminescent device using the same |
| KR20110054225A (en) * | 2009-11-17 | 2011-05-25 | 주식회사 이엘엠 | Organic light emitting material and organic light emitting diode having the same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557440A (en) * | 2015-02-05 | 2015-04-29 | 江西冠能光电材料有限公司 | Substituted benzophenanthrene derivative organic light emitting diode material |
| WO2017209297A1 (en) * | 2016-06-02 | 2017-12-07 | 国立大学法人名古屋大学 | Triarylene compound and method for producing same |
| WO2023085877A1 (en) * | 2021-11-15 | 2023-05-19 | 주식회사 엘지화학 | Compound and organic light-emitting element comprising same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhu et al. | Solution-processable single-material molecular emitters for organic light-emitting devices | |
| CN103951621B (en) | A kind of blue Organic Light Emitting Diode material | |
| CN105670610B (en) | The compound of organic photoelectric device and organic photoelectric device comprising the compound | |
| CN105418533B (en) | A kind of feux rouges thermal activation delayed fluorescence material and organic electroluminescence device | |
| CN104557440A (en) | Substituted benzophenanthrene derivative organic light emitting diode material | |
| KR101247626B1 (en) | Compounds for organic photoelectric device and organic photoelectric device containing the same | |
| Dong et al. | Spiro-annulated triarylamine-based hosts incorporating dibenzothiophene for highly efficient single-emitting layer white phosphorescent organic light-emitting diodes | |
| Guan et al. | Bright red light-emitting electroluminescence devices based on a functionalized europium complex | |
| CN103694277A (en) | Red-phosphorescence organic light emitting diode (LED) | |
| CN102421868A (en) | Compound for organic photoelectric device and organic photoelectric device comprising same | |
| CN107017349B (en) | Organic light-emitting display device | |
| CN102459506A (en) | Compound for an organic photoelectric element, and an organic photoelectric element comprising the same | |
| KR101865606B1 (en) | Condensed aryl compounds and organic light-diode including the same | |
| Zhou et al. | Efficient solution-processed red organic light-emitting diode based on an electron-donating building block of pyrrolo [3, 2-b] pyrrole | |
| Du et al. | Hot‐Exciton Mechanism and AIE Effect Boost the Performance of Deep‐Red Emitters in Non‐Doped OLEDs | |
| CN106611823B (en) | A kind of cross-linking organic semiconductor material of main part and its Organic Light Emitting Diode application | |
| CN106816544B (en) | A kind of cross-linking bipolarity organic semiconductor and its Organic Light Emitting Diode application | |
| CN104004026A (en) | Electronegative phosphor material | |
| CN104447505B (en) | Stable organic light emitting diode | |
| CN105111243A (en) | Light-emitting metal iridium complex and organic electroluminescence device prepared from same | |
| Peng et al. | Efficient non-doped blue fluorescent OLEDs based on bipolar phenanthroimidazole-triphenylamine derivatives | |
| CN104326971B (en) | A kind of thermostability Organic Electricity negativity quasiconductor | |
| Zhang et al. | Improving the efficiency of exciplex based OLEDs by controlling the different configurations of the donor | |
| CN101265260A (en) | Imidazopyrimidine-based compound and organic light-emitting device employing organic layer including the same | |
| CN104086524A (en) | Heat-resistant organic semiconductor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141224 |
|
| RJ01 | Rejection of invention patent application after publication |