CN103409133B - A kind of electroluminescent material and application thereof - Google Patents
A kind of electroluminescent material and application thereof Download PDFInfo
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- CN103409133B CN103409133B CN201310302427.2A CN201310302427A CN103409133B CN 103409133 B CN103409133 B CN 103409133B CN 201310302427 A CN201310302427 A CN 201310302427A CN 103409133 B CN103409133 B CN 103409133B
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- 239000000463 material Substances 0.000 title claims abstract description 65
- 238000005401 electroluminescence Methods 0.000 claims description 19
- 230000005540 biological transmission Effects 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 abstract description 13
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 8
- 150000002220 fluorenes Chemical class 0.000 abstract description 6
- 230000007704 transition Effects 0.000 abstract description 2
- 238000004020 luminiscence type Methods 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- -1 aldehyde radical Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 125000000753 cycloalkyl group Chemical group 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- 125000005429 oxyalkyl group Chemical group 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 125000002769 thiazolinyl group Chemical group 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical group ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- 239000004305 biphenyl Substances 0.000 description 4
- 235000010290 biphenyl Nutrition 0.000 description 4
- 125000004093 cyano group Chemical group *C#N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000000859 sublimation Methods 0.000 description 4
- 230000008022 sublimation Effects 0.000 description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 1
- 240000008168 Ficus benjamina Species 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001638 boron Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 150000003217 pyrazoles Chemical class 0.000 description 1
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Electroluminescent Light Sources (AREA)
Abstract
The present invention relates to a kind of electroluminescent material and application thereof, electroluminescent material of the present invention is centered by spiral shell two fluorenes, connect 4 groups containing quinoline, form distortion nonplanar structure, effectively prevent intermolecular gathering, the sterically hindered compound that makes of molecule itself has extraordinary film-forming properties and very high second-order transition temperature, so have the good electroluminescent fluorescent characteristics of luminescence and thermostability.Electroluminescent material of the present invention has applicable molecular entergy level, for the luminescent layer of blue organic electroluminescent device, can be used as the emitting layer material of blue organic electroluminescent device.
Description
Technical field
The present invention relates to a kind of electroluminescent material and application thereof, be specifically related to a kind of small molecule emitter material containing spiral shell two fluorenes and quinoline, and relate to the application of this material in blue-fluorescence field of organic electroluminescence.
Background technology
As flat panel display of new generation, organic electroluminescence device (OLED) because there is active illuminating, response is fast, visible angle is large, Flexible Displays can be realized and the advantage such as manufacture craft is simple, become the most favourable rival of technique of display of future generation, be subject to great attention that is academic and industrial community.Due to all circles' lasting input for many years and unremitting effort, organic electroluminescent technology has had and has greatly developed, and nowadays, has had and has much achieved industrialization based on the commodity of OLED technique of display.
Practical and the market-oriented key issue of current obstruction OLED be device luminous efficiency compared with low, working life is short, volume production difficulty is large.Exploitation high-level efficiency and the stable electroluminescent organic material of production, explore new device preparation technology, optimised devices structure, improve device efficiency and life-span and explore the preferred plan etc. of colorize, remain the major objective of research work.
Material for organic electroluminescence device mainly comprises electrode materials, carrier transmission material, luminescent material.Electrode materials is divided into cathode material and anode material, and carrier transmission material comprises electron transport material and hole mobile material.Luminescent material is most important material in OLED, and general luminous organic material should meet the following conditions:
1. the fluorescent characteristic of high-quantum efficiency, fluorescence spectrum is mainly distributed in the visible region of 400-700nm;
2. good characteristic of semiconductor, namely has high electric conductivity, energy conduction electron, or energy conduction hole, or both have concurrently;
3. good film-forming properties, does not produce pin hole in the thin layer of tens nano thickness;
4. good thermostability.In addition, the light stability of material is also very important.
In order to realize full-color display, need the luminescent material of red, green, blue three kinds of colors respectively.At present, red light material and green light material can meet practical needs, and the blue emitting material of efficient stable is still less, and it is lower to there is luminous efficiency, the problems such as work-ing life is relatively short, this have impact on the development of organic electroluminescence device to a great extent.
In OLED research, blue emitting material is required, and itself can prepare the Nan dian Yao of one of three primary colours as luminescent layer, other luminescent materials can also be entrained in blue emitting material and obtain green and red luminescent device.Blue emitting material generally has wide energy gap, and its electron affinity (EA) and the first ionization energy (IP) will mate.Blue emitting material requires that in molecular designing the chemical structure of material has conjugation to a certain degree, but the moment of dipole of molecule can not be too large, otherwise the easy red shift of luminescent spectrum is to green Region.Current blue emitting material mainly contains the fragrant blue light material of a carbon containing and hydrogen two kinds of elements, arylamine class blue light material, organic boron class blue light material and other blue light materials.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of electroluminescent material and application thereof, and the compounds of this invention, as blue-fluorescence luminescent material, in organic electroluminescence device, can obtain the novel materials for electroluminescence of high efficiency blue.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of electroluminescent material, has as shown in the formula the structure shown in 1:
Formula 1
Wherein, described R is any one in following structural formula:
R
1be selected from hydrogen, 1 ~ 5 carbon alkyl, containing a kind of in oxyalkyl, cycloalkyl, thiazolinyl, ester group, amide group, trifluoromethyl, benzene, biphenyl, cyano group, nitro, aldehyde radical, amino, hydroxyl, heterogeneous ring compound, halogen or their arbitrary combination.
R
2be selected from hydrogen, 1 ~ 5 carbon alkyl, containing a kind of in oxyalkyl, cycloalkyl, thiazolinyl, ester group, amide group, trifluoromethyl, benzene, biphenyl, cyano group, nitro, aldehyde radical, amino, hydroxyl, heterogeneous ring compound, halogen or their arbitrary combination.
R
3be selected from hydrogen, 1 ~ 5 carbon alkyl, containing a kind of in oxyalkyl, cycloalkyl, thiazolinyl, ester group, amide group, trifluoromethyl, benzene, biphenyl, cyano group, nitro, aldehyde radical, amino, hydroxyl, heterogeneous ring compound, halogen or their arbitrary combination.
R
4be selected from hydrogen, 1 ~ 5 carbon alkyl, containing a kind of in oxyalkyl, cycloalkyl, thiazolinyl, ester group, amide group, trifluoromethyl, benzene, biphenyl, cyano group, nitro, aldehyde radical, amino, hydroxyl, heterogeneous ring compound, halogen or their arbitrary combination.
Wherein, R
1, R
2, R
3and R
4in have at least one to be selected from hydrogen.
On the basis of technique scheme, the present invention can also do following improvement:
Further, the alkyl of described 1 ~ 5 carbon is the one in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl;
Further, described is one in methoxyl group, oxyethyl group, positive propoxy containing oxyalkyl;
Further, described cycloalkyl is the one in cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane;
Further, described thiazolinyl is the one in vinyl, propenyl, allyl group;
Further, described ester group is the one in methyl esters, ethyl ester, propyl ester, positive butyl ester, isobutyl ester;
Further, described heterogeneous ring compound is the one in pyrroles, furans, thiophene, imidazoles, thiazole, oxazole, pyrazoles, pyridine, pyrimidine, pyridazine, pyrazine, triazole.
Electroluminescent material preferred structure of the present invention is as follows:
The preparation method of electroluminescent material of the present invention is as follows:
By 2,2 ', 7,7 '-tetrabromo spiral shell two fluorenes carries out Suzuki linked reaction from the boric acid of the quinoline of different the position of substitution respectively, obtains the target compound shown in formula 1.
In above-mentioned steps, Suzuki linked reaction is carried out under nitrogen protection, and catalyzer is Pd (PPh
3)
4or palladium, temperature of reaction 60 ~ 100 DEG C, 12 ~ 36 hours reaction times.
By aforesaid method, for compound 4QL3SF (a) and 4QL4SF (b), seemingly, the reaction process preparing luminescent material is as follows for other compounds:
Present invention also offers a kind of application of above-mentioned electroluminescent material, described electroluminescent material uses, for the preparation of organic electroluminescence device as the emitting layer material in organic electroluminescence device.Described organic electroluminescence device is a kind of blue light organic electroluminescence device, and its structure comprises: the ITO Conducting Glass (anode) superposed successively, hole transmission layer (NPB), luminescent layer (4QL3SF), electron transfer layer (Alq
3), electron injecting layer (LiF) and cathode layer (Al); Wherein, described luminescent layer is above-mentioned electroluminescent material.All functions layer all adopts vacuum evaporation process to make.The molecular structural formula of some organic compound used in organic electroluminescence device is as follows:
The functional layer of organic electroluminescence device of the present invention is not limited to use above-mentioned materials, and these materials can replace with other materials, and to device performance to be further improved, as hole transmission layer can with replacements such as TPD, electron transfer layer can with replacements such as TPBI.The molecular structural formula of these materials is as follows:
Electroluminescent material of the present invention is applied in blue organic electroluminescent device, demonstrates higher efficiency, and its feature is:
1. be connected with 4 quinoline with spiral shell two fluorenes, take into account both advantages, at a right angle between the group of spiro atom both sides, the rigidity of molecule increased and reduces intermolecular accumulation, improve thermostability, and improve film-forming properties, and be there is by introducing 4 the quinoline group of conjugated structure, can molecular mass be increased, improve second-order transition temperature, increase molecular heat stability.Material of the present invention has applicable molecular entergy level, can be used as the blue emitting material in organic electroluminescence device.
2. there is good electroluminescence characters.The compounds of this invention is the blue organic electroluminescent device of luminescent material, the peak wavelength 433-445nm of device, CIE coordinate (0.17,0.19), high-high brightness 1200-2300cd/m
2.
Accompanying drawing explanation
Fig. 1 is the uv-visible absorption spectra of 4QL3SF in chloroformic solution prepared of embodiment 1 and fluorescence emission spectrum;
Fig. 2 is using 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, the voltage-current density curve of device;
Fig. 3 is using 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, the voltage-brightness curve of device;
Fig. 4 is using 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, the current density-current efficiency curve of device;
Fig. 5 is using 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, current density-effect rate curve of device;
Fig. 6 is using 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, and device is 2600cd/m in brightness
2time electroluminescent spectrum figure;
Fig. 7 is the uv-visible absorption spectra of 4QL4SF in chloroformic solution and fluorescence emission spectrum prepared according to embodiment 3;
Embodiment
Be described principle of the present invention and feature below in conjunction with accompanying drawing, example, only for explaining the present invention, is not intended to limit scope of the present invention.
The preparation of embodiment 1 luminescent material 4QL3SF and character
The synthesis of 1 luminescent material 4QL3SF
In 250mL there-necked flask, add 1.02g2,2 ', 7,7 '-tetrabromo spiral shell two fluorenes (1.6mmol) and 1.14g quinoline-3-boric acid (6.6mmol), add mixed solvent (70mL toluene, 30mL ethanol), then add 0.28gK
2cO
3, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, adds Pd (PPh
3)
40.03g(0.16mmol), reflux under strong stirring, successive reaction 24h.50mL water is added in reaction solution, 150mL ethyl acetate, separatory, collects organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, and eluent is ethyl acetate: normal hexane (1:10), obtains 0.52g yellow solid, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 350 DEG C, obtains the faint yellow target compound of 0.40g, productive rate 30%.
1HNMR(CDCl3,TMS,δ):9.069-9.073（d,4H，J=2.0Hz）,8.124-8.180(dd,4H),8.044-8.061(d,4H，J=8.5Hz),7.851-7.867(d,4H，J=8.0Hz),7.767-7.783(d,4H，J=8.0Hz),7.636-7.666(m,4H),7.483-7.513(m,4H),7.224-7.258(d,4H，J=17.0Hz).
High resolution mass spectrum: molecular formula C
61h
36n
4, theoretical value 824.2940, test value 824.3013.
The uv-visible absorption spectra of 24QL3SF and fluorescence spectrum
As shown in Figure 1, the solvent of use is chloroform for the uv-visible absorption spectra of 4QL3SF sterling under solution state and fluorescence spectrum.The fluorescence spectrum main peak 435nm of 4QL3SF is blue-light-emitting.
The application of embodiment 2 luminescent material 4QL3SF in organic electroluminescence device
The present embodiment prepares blue organic electroluminescent device by the following method:
A) ITO(tin indium oxide is cleaned) glass: clean ito glass each 30 minutes with deionized water, acetone, EtOH Sonicate respectively, then in plasma cleaner, process 5 minutes;
B) vacuum evaporation hole transmission layer NPB on anode ito glass, thickness is 50nm;
C) on hole transmission layer NPB, vacuum evaporation luminescent layer 4QL3SF, thickness is 30nm;
D) on luminescent layer 4QL3SF, vacuum evaporation electron transfer layer Alq
3, thickness is 30nm;
E) at electron transfer layer Alq
3on, vacuum evaporation electron injecting layer LiF, thickness is 1nm;
F) on electron injecting layer LiF, vacuum evaporation negative electrode Al, thickness is 100nm.
The structure of device is ITO/NPB (50nm)/4QL4SF (30nm)/Alq
3(30nm)/LiF (1nm)/Al (100nm).Using the 4QL3SF of embodiment 1 preparation as the luminescent layer of this device, as shown in Figure 2, as shown in Figure 3, as shown in Figure 4, current density-effect rate curve as shown in Figure 5 for current density-current efficiency curve for voltage-brightness curve for the voltage-current density curve of this device.The bright voltage that opens of device is 5.0V, and high-high brightness reaches 1250cd/m
2, maximum current efficiency .0.35cd/A, effect rate 0.14lm/W.Fig. 6 is this device is 1250cd/m in brightness
2time electroluminescent spectrum figure, CIE coordinate is positioned at (0.17,0.19).
The preparation of embodiment 3 luminescent material 4QL4SF and character:
The synthesis of 1 luminescent material 4QL4SF
In 250mL there-necked flask, add 1.02g2,2 ', 7,7 '-tetrabromo spiral shell two fluorenes (1.6mmol) and 1.14g quinoline-4-boric acid (6.6mmol), add mixed solvent (70mL toluene, 30mL ethanol), then add 0.28gK
2cO
3, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, adds Pd (PPh
3)
40.03g(0.16mmol), reflux under strong stirring, successive reaction 24h.50mL water is added in reaction solution, 150mL ethyl acetate, separatory, collects organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, and eluent is ethyl acetate: normal hexane (1:10), obtains 0.60g yellow solid, use the further sublimation purification of chemical gas-phase deposition system, sublimation temperature 350 DEG C, obtains the faint yellow target compound of 0.48g, productive rate 36%.
High resolution mass spectrum: molecular formula C
61h
36n
4, theoretical value 824.2940, test value 824.3021.
The uv-visible absorption spectra of 24QL4SF and fluorescence spectrum
As shown in Figure 7, the solvent of use is chloroform for the uv-visible absorption spectra of 4QL4SF sterling under solution state and fluorescence spectrum.The fluorescence spectrum main peak 439nm of 4QL4SF is blue-light-emitting.
The present invention aims to provide a kind of blue light material efficiently, using material provided by the present invention as the OLED of luminescent layer.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (3)
1. an electroluminescent material, is characterized in that, has structure as follows:
2. an application for electroluminescent material according to claim 1, is characterized in that, described electroluminescent material uses, for the preparation of organic electroluminescence device as the emitting layer material in organic electroluminescence device.
3. the application of electroluminescent material according to claim 2, it is characterized in that, described organic electroluminescence device is a kind of blue light organic electroluminescence device, its structure comprises: the ITO Conducting Glass, the hole transmission layer that superpose successively, luminescent layer, electron transfer layer, electron injecting layer and cathode layer;
Wherein, described luminescent layer is electroluminescent material according to claim 1.
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| CN104844464B (en) * | 2015-03-13 | 2016-08-24 | 中节能万润股份有限公司 | A kind of 9,9 '-Spirobifluorene dendrimer and preparation method and application |
| CN105859678B (en) * | 2016-03-29 | 2018-06-19 | 中节能万润股份有限公司 | A kind of hole mobile material of the group containing benzodioxane and its preparation method and application |
| CN108467367B (en) * | 2018-03-26 | 2019-03-15 | 广东工业大学 | A kind of imidazoles blue light material, crystal and the preparation method of two fluorenes containing spiral shell |
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| US20030168970A1 (en) * | 2000-11-24 | 2003-09-11 | Tsuyoshi Tominaga | Luminescent element material and luminescent element comprising the same |
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