CN101654430B - Broadband electron transport material and preparation and application - Google Patents
Broadband electron transport material and preparation and application Download PDFInfo
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- CN101654430B CN101654430B CN2009100927454A CN200910092745A CN101654430B CN 101654430 B CN101654430 B CN 101654430B CN 2009100927454 A CN2009100927454 A CN 2009100927454A CN 200910092745 A CN200910092745 A CN 200910092745A CN 101654430 B CN101654430 B CN 101654430B
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 125000003118 aryl group Chemical group 0.000 claims abstract description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 22
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 230000027756 respiratory electron transport chain Effects 0.000 claims description 19
- -1 aryl chlorobenzene Chemical compound 0.000 claims description 14
- 230000005540 biological transmission Effects 0.000 claims description 12
- 239000011521 glass Substances 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 7
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000001499 aryl bromides Chemical class 0.000 claims description 5
- 238000002347 injection Methods 0.000 claims description 5
- 239000007924 injection Substances 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 125000003774 valeryl group Chemical group O=C([*])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- XYOVOXDWRFGKEX-UHFFFAOYSA-N azepine Chemical compound N1C=CC=CC=C1 XYOVOXDWRFGKEX-UHFFFAOYSA-N 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims 3
- 125000002785 azepinyl group Chemical group 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 37
- WOLVEMPZUIFSII-IHHOKICGSA-N (2e,4e)-n-[(2s,5s)-5-(hydroxymethyl)-1-methyl-3-oxo-2-propan-2-yl-2,4,5,6-tetrahydro-1,4-benzodiazocin-8-yl]-5-[4-(trifluoromethyl)phenyl]penta-2,4-dienamide Chemical compound CN([C@H](C(N[C@H](CO)CC1=C2)=O)C(C)C)C1=CC=C2NC(=O)\C=C\C=C\C1=CC=C(C(F)(F)F)C=C1 WOLVEMPZUIFSII-IHHOKICGSA-N 0.000 description 35
- 101100046776 Arabidopsis thaliana TPPB gene Proteins 0.000 description 35
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- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 7
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
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- 238000002189 fluorescence spectrum Methods 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 4
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- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
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- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
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- QCKHVNQHBOGZER-UHFFFAOYSA-N 1,2,4,5-tetrabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C=C1Br QCKHVNQHBOGZER-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JTEUQFURLJKAMI-UHFFFAOYSA-N 1-phenylbenzo[a]anthracene Chemical compound C1(=CC=CC2=CC=C3C=C4C=CC=CC4=CC3=C12)C1=CC=CC=C1 JTEUQFURLJKAMI-UHFFFAOYSA-N 0.000 description 1
- IMRWILPUOVGIMU-UHFFFAOYSA-N 2-bromopyridine Chemical compound BrC1=CC=CC=N1 IMRWILPUOVGIMU-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- BSDGZUDFPKIYQG-UHFFFAOYSA-N 4-bromopyridine Chemical compound BrC1=CC=NC=C1 BSDGZUDFPKIYQG-UHFFFAOYSA-N 0.000 description 1
- LTUJKAYZIMMJEP-UHFFFAOYSA-N 9-[4-(4-carbazol-9-yl-2-methylphenyl)-3-methylphenyl]carbazole Chemical compound C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(C=2C(=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C)C(C)=C1 LTUJKAYZIMMJEP-UHFFFAOYSA-N 0.000 description 1
- CTZSHMSUEPKAEX-UHFFFAOYSA-N C(C1)C=Cc2c1c(CCC=C1)c1[n]2-c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n]1c(cccc2)c2c2ccccc12 Chemical compound C(C1)C=Cc2c1c(CCC=C1)c1[n]2-c(cc1)ccc1N(c(cc1)ccc1-[n]1c2ccccc2c2c1cccc2)c(cc1)ccc1-[n]1c(cccc2)c2c2ccccc12 CTZSHMSUEPKAEX-UHFFFAOYSA-N 0.000 description 1
- 101100100081 Oryza sativa subsp. japonica TPP3 gene Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWFGARXUJNKOMY-UHFFFAOYSA-N [3,5-di(carbazol-9-yl)phenyl]-triphenylsilane Chemical compound C1=CC=CC=C1[Si](C=1C=C(C=C(C=1)N1C2=CC=CC=C2C2=CC=CC=C21)N1C2=CC=CC=C2C2=CC=CC=C21)(C=1C=CC=CC=1)C1=CC=CC=C1 GWFGARXUJNKOMY-UHFFFAOYSA-N 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- XLGLMVCAOMQNJT-UHFFFAOYSA-N boric acid;chlorobenzene Chemical compound OB(O)O.ClC1=CC=CC=C1 XLGLMVCAOMQNJT-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000003810 ethyl acetate extraction Methods 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
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- JVZRCNQLWOELDU-UHFFFAOYSA-N gamma-Phenylpyridine Natural products C1=CC=CC=C1C1=CC=NC=C1 JVZRCNQLWOELDU-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
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- BBFCIBZLAVOLCF-UHFFFAOYSA-N pyridin-1-ium;bromide Chemical compound Br.C1=CC=NC=C1 BBFCIBZLAVOLCF-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention discloses a broadband electron transport material and the preparation and application; the material takes 1,2,4,5,-tetraphenyl benzene as a core, four aryl groups are connected at the periphery of the core to obtain a chemical compound with a swastika structure, higher steric hindrance leads aromatic rings to be arrayed in a twisting way, and the whole molecule is in a non-planar structure, thereby avoiding aggregation and mutual effect among moleculars and having higher energy band. The heat stability of the material is good, and the broadband electron transport material has good electron transporting capacity and cavity sopping power, and can be used as an electron transporting layer of a blue phosphorescence organic electrochriomic device, thereby greatly improving the efficiency of the device.
Description
Technical field
The present invention relates to organic electroluminescence device (OLED), the application of particularly a kind of broadband electron transport material and preparation method thereof, and this material in blue phosphorescent organic electroluminescent device.
Background technology
Organic electroluminescent is the flat panel display of new generation of generally acknowledging at present the practical prospect of tool, have the material range of choice wide, can realize by blue light region to the full color of red light district show, driving voltage is low, luminosity and luminous efficiency height, the visual angle is wide, response speed is fast, can realize plurality of advantages such as flexibility demonstration.In organic electroluminescent, electronics and hole the compound and organic molecule that excites is not spinned and selects the restriction of law, in theory according to statistical distribution, the ratio that produces excited triplet state and excited singlet state is 3: 1.Therefore in the fluorescence electroluminescent, there is 75% excited energy to lose.If yet utilize the phosphorescence electroluminescent material, just can make full use of all excited state, thereby promote OLED efficient to increase substantially.In panchromatic demonstration field, blue light is as one of three primary colours, and the important component part of white light still not can be used as exciting light to realize the demonstration of green glow and ruddiness yet.But the blue phosphorescent luminescent material is compared and green and ruddiness phosphorescent light-emitting materials, owing to can be with broad, current carrier injection and exciton restriction be difficulty relatively, causes efficient lower.
Usually, in semiconducter device, the transmission rate in hole will be higher than electronics far away, and in order to obtain better efficient, developing more effective electron transport material is very important for the efficient that improves electroluminescent device.At present, the blue phosphorescent device generally adopts FIrpic as luminous object, and the electron transport material in the device generally adopts TAZ, BPhen, BCP etc.In the blue phosphorescent device, the phosphorescence object has higher triplet, come blocking hole further to pass with electron transport material to negative electrode with higher triplet, thereby triplet excitons is limited in luminescent layer, the efficient of raising blue phosphorescent organic electroluminescent device that can be to a great extent.In a word, develop the novel electron transport material that is used for blue phosphorescent organic electroluminescent, generally need satisfy following two kinds of requirements: 1, high triplet, good confinement triplet excitons; 2, good electron transmission rate guarantees carrier balance.
Though a lot of OLED electron transport materials have been arranged at present, can be used in the blue phosphorescent electroluminescent and to satisfy the electron transport material of above condition also rare.
Summary of the invention
The object of the present invention is to provide a kind of compound that can be used as broadband electron transport material, this compound is used for blue phosphorescent organic electroluminescent device, can significantly improve the efficient of blue phosphorescent device.
Another object of the present invention provides the preparation method of above-mentioned electron transport material.
The 3rd purpose of the present invention provides the application of above-mentioned electron transport material in blue phosphorescent organic electroluminescent device.
Electron transport material of the present invention, be structural formula as shown in the formula the compound shown in the I, abbreviate TPPB as:
Formula I
Wherein R is an aryl, comprises non-heterocyclic aryl and heterocyclic aryl, preferred nitrogen heterocyclic aryl, most preferably azepine six-ring aryl and azepine five-ring aryl, for example pyridyl
The preparation method of above-mentioned electron transport material comprises the steps:
(1) the Suzuki reaction by m-chloro phenylo boric acid and aryl bromide makes an aryl chlorobenzene;
(2) an aryl chlorobenzene is carried out acid esterification, make an aryl borate ester;
(3) by 1,2,4, the Suzuki of a 5-tetrabromo-benzene and aryl borate ester reaction makes the compound shown in the formula I.
Wherein, the reaction of above-mentioned steps (1) generally is to carry out under the protection of nitrogen or rare gas element, with Pd (PPh
3)
4(tetrakis triphenylphosphine palladium) or palladium are catalyzer, and m-chloro phenylo boric acid and aryl bromide (for example pyridine bromide, i.e. 2-bromopyridine or 3-bromopyridine or 4-bromopyridine) were in 80-100 ℃ of back flow reaction 12-36 hour.
The reaction of above-mentioned steps (2) is under the protection of nitrogen or rare gas element, carries out in the anhydrous environment, at Pd (dba)
2Under the catalysis of (two (dibenzalacetone) palladium), an aryl chlorobenzene and two valeryl two boron were in 70-90 ℃ of back flow reaction 48-96 hour.
The reaction of above-mentioned steps (3) is under the protection of nitrogen or rare gas element, with Pd (PPh
3)
4Or palladium is catalyzer, 1,2,4, and a 5-tetrabromo-benzene and an aryl borate ester were at 80-100 ℃ of back flow reaction 12-36 hour.
With R be
Be example, the flow process of the preparation feedback of electron transport material TPPB is as follows:
Guarantee the good electron transmission rate, need aromatic yl groups such as pyridine, quinoline in the molecule, but will obtain high triplet, just need suppress pi-conjugated system as far as possible, reduce the conjugation degree.Have the group of high triplet and electron transport ability concurrently, for example phenylpyridine is the good candidate of blue phosphorescent electron transport material molecular designing.The present invention adopts 1,2,4, and 5-tetraphenyl benzene connects four aromatic yl groups on every side for nuclear, obtains “ Swastika " font broadband electron transport material TPPB.This electron transport material has good electron transmittability and hole barrier ability concurrently.
Above-mentioned electron transport material provided by the invention can be used for preparing the electron transfer layer of blue phosphorescent electroluminescent device.Prepared blue phosphorescent device generally comprises synergetic successively ITO Conducting Glass (anode), hole injection layer (PEODT:PSS), hole transmission layer (TPD or TCTA), luminescent layer (mCP﹠amp; FIrpic), electron transfer layer (TPPB), electron injecting layer (LiF) and cathode layer (Al).Except that hole injection layer PEDOT:PSS and hole transmission layer TPD employing spin coating legal system film, other functional layers all can adopt the vacuum evaporation filming technology.The molecular structural formula of more used organic compound is as follows in this device:
Certainly, the functional layer of device of the present invention does not limit the use above-mentioned materials, these materials can replace with other materials, can use 4BTPD, 3BTPD such as hole transmission layer, DTASi etc., main body can be used CDBP, SimCP, 35DczPPy etc., and the blue phosphorescent object can also be used Fir6, Firtaz, FIrN4 etc., and the molecular structural formula of these materials is as follows:
Electron transport material of the present invention is applied in the blue phosphorescent organic electroluminescent, has significantly improved the efficient of device, and it has tempting prospect in the application of blue phosphorescent organic electroluminescent device.The major advantage of this material is:
1, the employing 1 of this material, 2,4,5-tetraphenyl benzene connects four aromatic yl groups on every side for nuclear, forms “ Swastika " font structure; higher steric hindrance makes mutual aligned twisted between the aromatic ring; whole molecule becomes nonplanar structure, avoids intermolecular gathering and interaction, and has higher can be with (4.0eV);
2, this material has good thermostability, and wherein R is
The TPPB decomposition temperature be higher than 400 ℃, second-order transition temperature is up to 97 ℃;
3, the HOMO energy level of this material has the function of hole barrier about 6.4eV;
4, the blue phosphorescent organic electroluminescent device with this material preparation has than higher efficient, and the maximum current efficient of device can reach 40.6cd/A, and corresponding maximum external quantum efficiency is 19.6%.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectrum of TPPB under tetrahydrofuran solution and solid film of embodiment 1 preparation, and the fluorescence spectrum figure of TPPB under tetrahydrofuran solution and solid film.
Fig. 2 be among the embodiment 2 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the voltage-to-current densimetric curve of device.
Fig. 3 be among the embodiment 2 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the voltage-brightness curve of device.
Fig. 4 be among the embodiment 2 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the current density of device-current efficiency curve.
Fig. 5 is that TPPB is as the electron transfer layer of blue phosphorescent organic electroluminescent device among the embodiment 2, and device is reaching 100cd/m
2The time normalization method electroluminescent spectrum figure.
Fig. 6 be among the embodiment 3 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the voltage-to-current densimetric curve of device.
Fig. 7 be among the embodiment 3 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the voltage-brightness curve of device.
Fig. 8 be among the embodiment 3 TPPB as the electron transfer layer of blue phosphorescent organic electroluminescent device, the current density of device-current efficiency curve.
Embodiment
Following examples further specify content of the present invention, but should not be construed as limitation of the present invention.
Embodiment 1 “ Swastika " preparation and the character of font broadband electron transport material TPPB
1, between synthetic-pyridine-3-chlorobenzene (compound 1)
Referring to above-mentioned reaction process 1,2.42g 3-bromopyridine (15.3mmol), 2.475g 3-chlorobenzene boric acid (15.8mmol) is put into there-necked flask, add 75mL toluene and 25mL ethanol again, stirring makes the solid dissolving, adds the 2M aqueous solution of 45mL salt of wormwood then, is warming up to 90 ℃, refluxed 1 hour, and added 0.35g Pd (PPh then
3)
4(0.305mmol); nitrogen protection continues reaction 24 hours down; reaction finishes the back and adds 100mL water; then with 200mL toluene extraction 3 times; organic layer mixes the back anhydrous magnesium sulfate drying; filter and revolve and steam afterwards with column chromatography purification (normal hexane: ethyl acetate=3: 1), obtain weak yellow liquid 2.65g (productive rate 91%).
1H?NMR(CDCl
3，TMS，δ)：7.36-7.47(m，4H)，7.56(s，1H)，7.83-7.86(m，1H)，8.62(dd，1H)，8.82(d，7H).
2, between synthetic-pyridine-3-phenylo boric acid (compound 2)
In two mouthfuls of flasks, mix two valeryl two boron (16.8mmol) of 4.26g, between 2.65g-pyridine-3-chlorobenzene (14.0mmol), 0.482g Pd (dba)
2(0.84mmol), 0.94g thricyclohexyl phosphorus (3.5mmol), 4.115g Potassium ethanoate (41.8mmol); logical nitrogen adds exsiccant 1,4-dioxane (75mL) about 10 minutes then; stir, be warming up to 80 ℃, nitrogen protection is 72 hours (referring to reaction process 1) of backflow down.Reaction finishes postcooling to room temperature, uses diatomite filtration.Filtrate is poured in the water and is used ethyl acetate extraction.Merge organic phase and use anhydrous magnesium sulfate drying.Thick product is done the eluent column chromatography with chloroform/ethyl acetate (6: 1) and is purified.Obtain yellow solid 3.8g (productive rate 80%)
1H?NMR(CDCl
3，TMS，δ)：1.37(s，12H)，7.35-7.39(m，1H)，7.51(t，1H)，7.67-7.70(m，1H)，7.86(d，1H)，7.95-7.92(m，7H)，8.02(s，1H)，8.60(dd，1H)，8.88(d，1H).
3, synthetic electron transport material TPPB
Referring to above-mentioned reaction process 2,0.67 g 1,2,4,5-tetrabromo-benzene (1.70mmol), 2.475g compound 2 (15.8mmol) is put into there-necked flask, adds 60mL toluene and 20mL ethanol again, stirs to make the solid dissolving, the 2M aqueous solution that adds 20mL salt of wormwood then, be warming up to 90 ℃, refluxed 1 hour, add 0.157g Pd (PPh then
3)
4(0.136mmol); nitrogen protection continues reaction 24 hours down; reaction finishes the back and adds 100mL water; use the 200mL chloroform extraction then 3 times; organic layer mixes the back anhydrous magnesium sulfate drying; filter and revolve steam the back with column chromatography purify (chloroform: methyl alcohol=30: 1), obtain faint yellow solid 0.97g, dry back with the vacuum-sublimation method purify white solid 0.4g (productive rate 34%).
1H?NMR(CDCl
3，TMS，δ)：8.56-8.53(t，8H)，7.74(s，2H)，7.64-7.62(d，4H)，7.52-7.42(m，16)，7.30-7.26(m，4H)；
13C?NMR(CDCl
3，TMS，δ)：148.37，148.04，141.34，139.67，137.61，136.35，134.37，132.60，129.47，129.20，129.14，125.77，123.52.
4, the uv-visible absorption spectra of TPPB and fluorescence spectrum
The uv-visible absorption spectra of prepared TPPB under solution and solid film as shown in Figure 1.The absorption spectrum of this TPPB in THF solution has only a peak that is positioned at 256nm, comes from π-π * transition.Compare red shift to some extent in absorption under the solid film and the solution, absorption peak is positioned at 263nm.Can be calculated by the ABSORPTION EDGE of this TPP3 in THF solution, it can be with and be 4.0eV.The fluorescence spectrum of this TPPB under solution and solid film also as shown in Figure 1.The fluorescence Spectra peak value of this TPPB in tetrahydrofuran solution is positioned at 382nm, and the fluorescence Spectra peak value of solid film is positioned at 384, and be very approaching with the fluorescence Spectra under the solution.
5, the electrochemical properties of TPPB
Electrochemical properties with the prepared TPPB of cyclic voltammetry test.Calculate the energy level of dyestuff with the benchmark of ferrocene, the HOMO energy level of this TPPB is-6.4eV, so it has the function of hole barrier concurrently in as electron transfer layer.Can draw according to the band of being calculated out by the ABSORPTION EDGE of absorption spectrum, the lumo energy of this TPPB is-2.4eV.
The application one of embodiment 2 electron transport material TPPB in blue phosphorescent organic electroluminescent device
Present embodiment prepares blue phosphorescent organic electroluminescent device according to following method:
A) clean ITO (tin indium oxide) glass: used deionized water, acetone, ethanol ultrasonic cleaning ito glass respectively respectively 15 minutes, and in the plasma clean device, handled 2 minutes then;
B) spin coating PEDOT:PSS is as hole injection layer on the anode ito glass, and rotating speed is 4000 rev/mins, in air 200 ℃ annealing 5 minutes, then in nitrogen 200 ℃ annealing 15 minutes, thickness is 28nm;
C) vacuum evaporation hole transmission layer TCTA on the PEDOT:PSS layer, speed 0.5-
Thickness is 40nm.
D) on hole transmission layer TCTA, common evaporation luminescent layer mCP and FIrpic, the shared mass ratio of FIrpic is 8%, total liquid evaporation rate is 1.0-
Thickness is 10nm;
E) at luminescent layer mCP﹠amp; Vacuum evaporation electron transfer layer TPPB on the FIrpic, speed 0.5-
Thickness 40nm;
F) vacuum evaporation LiF on electron transfer layer TPPB, speed
Thickness 0.5nm;
G) vacuum evaporation negative electrode Al on LiF, thickness is 120nm.
The structure of device is ITO/PEDOT:PSS (28nm)/TCTA (40nm)/mCP:FIrpic8% (10nm)/TPPB (40nm)/LiF (0.5nm)/Al (120nm).TPPB with embodiment 1 preparation is an electron transfer layer, and the voltage-to-current densimetric curve of this device and voltage-brightness curve is distinguished as shown in Figures 2 and 3, and current density-the current efficiency curve as shown in Figure 4.The bright voltage that opens of device is 4.2V, reaches 100cd/m during 4.8V
2, reach 1000cd/m during 5.1V
2, high-high brightness reaches 4390cd/m
2, maximum current efficient 19.4cd/A.Fig. 5 is that device is at 100cd/m
2The time electroluminescent spectrum figure, the CIE coordinate is positioned at (0.18,0.39).
The application two of embodiment 3 electron transport material TPPB in blue phosphorescent organic electroluminescent device
Present embodiment prepares blue phosphorescent organic electroluminescent device according to following method:
A) clean ITO (tin indium oxide) glass: used deionized water, acetone, ethanol ultrasonic cleaning ito glass respectively respectively 15 minutes, and in the plasma clean device, handled 2 minutes then;
B) spin coating TPD is as first hole transmission layer on the anode ito glass, and rotating speed is 2000 rev/mins, and thickness is 20nm;
C) the vacuum evaporation second hole transmission layer TCTA on the TPD layer, speed 0.5-
Thickness is 20nm.
D) on hole transmission layer TCTA, common evaporation luminescent layer mCP and FIrpic, the shared mass ratio of FIrpic is 8%, total liquid evaporation rate is 1.0-
Thickness is 20nm;
E) at luminescent layer mCP﹠amp; Vacuum evaporation electron transfer layer TPPB on the FIrpic, speed 0.5-
Thickness 30nm;
F) vacuum evaporation LiF on electron transfer layer TPPB, speed
Thickness 0.5nm;
G) vacuum evaporation negative electrode Al on LiF, thickness is 120nm.
The structure of device is ITO/TPD (20nm)/TCTA (20nm)/mCP:FIrpic8% (20nm)/TPPB (30nm)/LiF (0.5nm)/Al (120nm).TPPB with embodiment 1 preparation is an electron transfer layer, and the voltage-to-current densimetric curve of this device and voltage-brightness curve is distinguished as shown in Figure 6 and Figure 7, and current density-the current efficiency curve as shown in Figure 8.The bright voltage that opens of device is 3.4V, reaches 100cd/m during 4.4V
2, reach 1000cd/m during 5.7V
2, high-high brightness reaches 19800cd/m
2, maximum current efficient 40.6cd/A, maximum external quantum efficiency 19.6%.The electroluminescent spectrum of device and CIE coordinate are with embodiment 2.
Claims (12)
1. the compound shown in the formula I:
Formula I
Among the formula I, R is azepine six-ring aryl or azepine five-ring aryl.
2. compound as claimed in claim 1 is characterized in that R is
3. the preparation method of claim 1 or 2 described compounds may further comprise the steps:
1) the Suzuki reaction by m-chloro phenylo boric acid and aryl bromide makes an aryl chlorobenzene;
2) an aryl chlorobenzene is carried out acid esterification, make an aryl borate ester;
3) by 1,2,4, the Suzuki of a 5-tetrabromo-benzene and aryl borate ester reaction makes the compound shown in the formula I.
4. preparation method as claimed in claim 3 is characterized in that, described step 1) is under protection of nitrogen gas, with Pd (PPh
3)
4Or palladium is catalyzer, and m-chloro phenylo boric acid and aryl bromide were in 80-100 ℃ of back flow reaction 12-36 hour.
5. preparation method as claimed in claim 3 is characterized in that, described step 1) is under the protection of rare gas element, with Pd (PPh
3)
4Or palladium is catalyzer, and m-chloro phenylo boric acid and aryl bromide were in 80-100 ℃ of back flow reaction 12-36 hour.
6. preparation method as claimed in claim 3 is characterized in that, described step 2) be under protection of nitrogen gas, in the anhydrous environment with Pd (dba)
2Be catalyzer, an aryl chlorobenzene and two valeryl two boron were in 70-90 ℃ of back flow reaction 48-96 hour.
7. preparation method as claimed in claim 3 is characterized in that, described step 2) be under the protection of rare gas element, in the anhydrous environment with Pd (dba)
2Be catalyzer, an aryl chlorobenzene and two valeryl two boron were in 70-90 ℃ of back flow reaction 48-96 hour.
8. preparation method as claimed in claim 3 is characterized in that, described step 3) is under protection of nitrogen gas, with Pd (PPh
3)
4Or palladium is catalyzer, 1,2,4, and a 5-tetrabromo-benzene and an aryl borate ester were at 80-100 ℃ of back flow reaction 12-36 hour.
9. preparation method as claimed in claim 3 is characterized in that, described step 3) is under the protection of rare gas element, with Pd (PPh
3)
4Or palladium is catalyzer, 1,2,4, and a 5-tetrabromo-benzene and an aryl borate ester were at 80-100 ℃ of back flow reaction 12-36 hour.
10. claim 1 or 2 described compounds are as the purposes of electron transport material.
11. a blue phosphorescent organic electroluminescent device comprises electron transfer layer, it is characterized in that, the material of described electron transfer layer is claim 1 or 2 described compounds.
12. blue phosphorescent organic electroluminescent device as claimed in claim 11 is characterized in that, this device comprises synergetic successively ITO Conducting Glass, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
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| JP5760323B2 (en) * | 2010-03-16 | 2015-08-05 | 東ソー株式会社 | 1,2,4,5-Substituted phenyl derivatives, process for producing the same, and organic electroluminescent device comprising them as constituents |
| WO2016204406A1 (en) * | 2015-06-19 | 2016-12-22 | 삼성에스디아이 주식회사 | Composition for organic photoelectronic element, organic photoelectronic element, and display apparatus |
| KR102059021B1 (en) | 2015-06-19 | 2019-12-24 | 삼성에스디아이 주식회사 | Composition for organic optoelectronic device, organic optoelectric device and display device |
| KR101919438B1 (en) | 2015-06-26 | 2018-11-16 | 삼성에스디아이 주식회사 | Composition for organic optoelectric device, organic optoelectric device and display device |
| KR101940169B1 (en) * | 2016-02-04 | 2019-01-18 | 삼성에스디아이 주식회사 | Organic compound for optoelectric device and organic optoelectric device and display device |
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