CN103409133A - Electroluminescent material and application thereof - Google Patents
Electroluminescent material and application thereof Download PDFInfo
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- CN103409133A CN103409133A CN2013103024272A CN201310302427A CN103409133A CN 103409133 A CN103409133 A CN 103409133A CN 2013103024272 A CN2013103024272 A CN 2013103024272A CN 201310302427 A CN201310302427 A CN 201310302427A CN 103409133 A CN103409133 A CN 103409133A
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- electroluminescent material
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- thiazolinyl
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- 239000000463 material Substances 0.000 title claims abstract description 68
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 24
- -1 aldehyde radical Chemical class 0.000 claims description 24
- 238000005401 electroluminescence Methods 0.000 claims description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 10
- 125000004185 ester group Chemical group 0.000 claims description 10
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 10
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 8
- 239000004305 biphenyl Substances 0.000 claims description 8
- 235000010290 biphenyl Nutrition 0.000 claims description 8
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 230000005540 biological transmission Effects 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 5
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 2
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004914 cyclooctane Substances 0.000 claims description 2
- 125000004494 ethyl ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000004702 methyl esters Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 claims description 2
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 2
- 229930192474 thiophene Natural products 0.000 claims description 2
- 150000003852 triazoles Chemical class 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 abstract description 8
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000009477 glass transition Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 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
- 238000000034 method Methods 0.000 description 6
- 238000007738 vacuum evaporation Methods 0.000 description 6
- 150000002220 fluorenes Chemical class 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 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 compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000003756 stirring Methods 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
- 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
- 239000003086 colorant Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 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
- 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
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 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
- 240000008168 Ficus benjamina Species 0.000 description 1
- 238000009825 accumulation Methods 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
- 239000010406 cathode material Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 230000008569 process Effects 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
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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Abstract
The invention relates to an electroluminescent material and an application thereof. The electroluminescent material treats spirobifluorene as a center and allows four quinoline-containing groups to be connected to form a distorted non-planar structure in order to effectively avoid the intermolecular aggregation, and the molecular steric hindrance makes a compound have a very good film forming ability and a very high glass transition temperature, so the electroluminescent material has a good electroluminescent characteristic and a good heat stability. The electroluminescent material has a suitable molecular energy grade, is used in the luminescent layers of blue organic electroluminescent devices, and can be used in the blue organic electroluminescent devices as a luminescent layer material.
Description
Technical field
The present invention relates to a kind of electroluminescent material and application thereof, be specifically related to a kind of small molecules luminescent material that contains spiral shell two fluorenes and quinoline, and relate to the application of this material in blue-fluorescence organic electroluminescent field.
Background technology
As flat panel display of new generation, organic electroluminescence device (OLED) because have active illuminating, response is fast, visible angle is large, can realize the advantages such as flexible demonstration and manufacture craft are simple, make its most favourable rival who becomes technique of display of future generation, be subject to the great attention of academic and industrial community.Due to all circles' lasting input and unremitting effort for many years, the organic electroluminescent technology has had greatly development, nowadays, has had much and has realized industrialization based on the commodity of OLED technique of display.
The luminous efficiency that hinders at present the practical and market-oriented key issue of OLED and be device than low, working life is short, the volume production difficulty is large.The stable electroluminescent organic material of exploitation high-level efficiency and production, explore new device preparation technology, optimised devices structure, improve the preferred plan of device efficiency and life-span and exploration colorize etc., 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, general luminous organic material should meet the following conditions:
1. the fluorescent characteristic of high-quantum efficiency, fluorescence spectrum mainly is distributed in the visible region of 400-700nm;
2. good characteristic of semiconductor, namely have high electric conductivity, energy conduction electron, or energy conduction hole, or both have concurrently;
3. good film-forming properties, do 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 demonstration, need respectively the luminescent material of three kinds of colors of red, green, blue.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 exist luminous efficiency, the problems such as work-ing life is relatively short, this has affected the development of organic electroluminescence device to a great extent.
In OLED research, blue emitting material is essential, itself can be used as the blue light OLED that luminescent layer prepares one of three primary colours, 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 the chemical structure of material to have conjugation to a certain degree on molecular designing, but the moment of dipole of molecule can not be too large, otherwise the easy red shift of luminescent spectrum is to green Region.Blue emitting material mainly contains fragrant blue light material, arylamine class blue light material, organic boron class blue light material and other blue light materials of a carbon containing and two kinds of elements of hydrogen at present.
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, for organic electroluminescence device, can obtain the novel materials for electroluminescence of efficient blue light.
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, contain 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, contain 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, contain 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, contain 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 a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl;
Further, the described oxyalkyl that contains is a kind of in methoxyl group, oxyethyl group, positive propoxy;
Further, described cycloalkyl is a kind of in cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane;
Further, described thiazolinyl is a kind of in vinyl, propenyl, allyl group;
Further, described ester group is a kind of in methyl esters, ethyl ester, propyl ester, positive butyl ester, isobutyl ester;
Further, described heterogeneous ring compound is a kind of 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 carry out the Suzuki linked reaction from the boric acid of the quinoline of different the position of substitution respectively, obtain the target compound shown in formula 1.
In above-mentioned steps, the Suzuki linked reaction is carried out under nitrogen protection, and catalyzer is Pd (PPh
3)
4Or palladium, 60～100 ℃ of temperature of reaction, 12～36 hours reaction times.
By aforesaid method, take compound 4QL3SF (a) and 4QL4SF (b) and be example, seemingly, the reaction process for preparing luminescent material is as follows for other compounds:
The present invention also provides a kind of application of above-mentioned electroluminescent material, and described electroluminescent material is as the luminescent layer materials'use in organic electroluminescence device, for the preparation of 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), hole transmission layer (NPB), luminescent layer (4QL3SF), the electron transfer layer (Alq that superpose successively
3), electron injecting layer (LiF) and cathode layer (Al); Wherein, described luminescent layer is above-mentioned electroluminescent material.The all functions layer all adopts vacuum evaporation process to make.In organic electroluminescence device, the molecular structural formula of organic compound more used 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, to device performance to be further improved, can be with replacements such as TPD as hole transmission layer, and electron transfer layer can be 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 characteristics are:
1. with spiral shell two fluorenes, be connected with 4 quinoline, take into account both advantages, between the group of spiro atom both sides, meet at right angles, make the rigidity of molecule increase and reduce intermolecular accumulation, improved thermostability, and improved film-forming properties, and by introducing 4 quinoline groups with conjugated structure, can increase molecular mass, 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. has electroluminescence characters preferably.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.
The accompanying drawing explanation
Fig. 1 is uv-visible absorption spectra and the fluorescence emission spectrum of 4QL3SF in chloroformic solution of embodiment 1 preparation;
Fig. 2 is usingd 4QL3SF as the luminescent layer of blue organic electroluminescent device, the voltage-to-current densimetric curve of device in embodiment 2;
Fig. 3 is usingd 4QL3SF as the luminescent layer of blue organic electroluminescent device, the voltage-brightness curve of device in embodiment 2;
Fig. 4 is usingd 4QL3SF as the luminescent layer of blue organic electroluminescent device, the current density of device-current efficiency curve in embodiment 2;
Fig. 5 is usingd 4QL3SF as the luminescent layer of blue organic electroluminescent device, the current density of device-effect rate curve in embodiment 2;
Fig. 6 is usingd 4QL3SF as the luminescent layer of blue organic electroluminescent device in embodiment 2, device is 2600cd/m in brightness
2The time electroluminescent spectrum figure;
Fig. 7 is uv-visible absorption spectra and the fluorescence emission spectrum of 4QL4SF in chloroformic solution according to embodiment 3 preparations;
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention and feature are described, example, only be used to explaining the present invention, is not intended to limit scope of the present invention.
Preparation and the character of embodiment 1 luminescent material 4QL3SF
1 luminescent material 4QL3SF's is synthetic
In the 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 adds 0.28g K
2CO
3, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, add Pd (PPh
3)
40.03g(0.16mmol), under strong stirring, reflux, successive reaction 24h.In reaction solution, add 50mL water, the 150mL ethyl acetate, separatory, collect organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, and eluent is ethyl acetate: normal hexane (1:10) obtains the 0.52g yellow solid, use the chemical gas-phase deposition system purification that further distils, 350 ℃ of sublimation temperatures, obtain the faint yellow target compound of 0.40g, productive rate 30%.
1H?NMR(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
The 4QL3SF sterling under solution state uv-visible absorption spectra and fluorescence spectrum as shown in Figure 1, the solvent used is chloroform.The fluorescence spectrum main peak 435nm of 4QL3SF, be blue-light-emitting.
The present embodiment prepares blue organic electroluminescent device by the following method:
A) clean the ITO(tin indium oxide) glass: used respectively deionized water, acetone, ethanol ultrasonic cleaning ito glass respectively 30 minutes, and then in the plasma clean device, processed 5 minutes;
B) vacuum evaporation hole transmission layer NPB on the anode ito glass, thickness is 50nm;
C) on hole transmission layer NPB, vacuum evaporation luminescent layer 4QL3SF, thickness are 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 are 1nm;
F) on electron injecting layer LiF, vacuum evaporation negative electrode Al, thickness are 100nm.
The structure of device is ITO/NPB (50nm)/4QL4SF (30nm)/Alq
3(30nm)/LiF (1nm)/Al (100nm).4QL3SF prepared by the embodiment 1 of usining is as the luminescent layer of this device, and as shown in Figure 2, as shown in Figure 3, as shown in Figure 4, current density-the effect rate curve as shown in Figure 5 for current density-current efficiency curve for voltage-brightness curve for the voltage-to-current densimetric 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 1250cd/m for this device in brightness
2The time electroluminescent spectrum figure, the CIE coordinate is positioned at (0.17,0.19).
Preparation and the character of embodiment 3 luminescent material 4QL4SF:
1 luminescent material 4QL4SF's is synthetic
In the 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 adds 0.28g K
2CO
3, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask, add Pd (PPh
3)
40.03g(0.16mmol), under strong stirring, reflux, successive reaction 24h.In reaction solution, add 50mL water, the 150mL ethyl acetate, separatory, collect organic phase, concentrating under reduced pressure, thick product carries out purifying through column chromatography, and eluent is ethyl acetate: normal hexane (1:10) obtains the 0.60g yellow solid, use the chemical gas-phase deposition system purification that further distils, 350 ℃ of sublimation temperatures, obtain 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
The 4QL4SF sterling under solution state uv-visible absorption spectra and fluorescence spectrum as shown in Figure 7, the solvent used is chloroform.The fluorescence spectrum main peak 439nm of 4QL4SF, be blue-light-emitting.
The present invention aims to provide a kind of efficient blue light material, usings the OLED device of material provided by the present invention as luminescent layer.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (5)
1. an electroluminescent material, is characterized in that, 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, contain 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, contain 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, contain 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, contain 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.
2. electroluminescent material according to claim 1, is characterized in that, the alkyl of described 1～5 carbon is a kind of in methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl;
The described oxyalkyl that contains is a kind of in methoxyl group, oxyethyl group, positive propoxy;
Described cycloalkyl is a kind of in cyclopropane, tetramethylene, pentamethylene, hexanaphthene, suberane, cyclooctane;
Described thiazolinyl is a kind of in vinyl, propenyl, allyl group;
Described ester group is a kind of in methyl esters, ethyl ester, propyl ester, positive butyl ester, isobutyl ester;
Described heterogeneous ring compound is a kind of in pyrroles, furans, thiophene, imidazoles, thiazole, oxazole, pyrazoles, pyridine, pyrimidine, pyridazine, pyrazine, triazole.
3. electroluminescent material according to claim 1, is characterized in that, has structure as follows:
4. the application according to the arbitrary described electroluminescent material of claim 1-3, is characterized in that, described electroluminescent material is as the luminescent layer materials'use in organic electroluminescence device, for the preparation of organic electroluminescence device.
5. the application of electroluminescent material according to claim 4, 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 the arbitrary described electroluminescent material of claim 1-3.
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