CN100441586C - Organic metal complex and organic electroluminescent apparatus containing said organic metal complex - Google Patents
Organic metal complex and organic electroluminescent apparatus containing said organic metal complex Download PDFInfo
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- CN100441586C CN100441586C CNB2004100857923A CN200410085792A CN100441586C CN 100441586 C CN100441586 C CN 100441586C CN B2004100857923 A CNB2004100857923 A CN B2004100857923A CN 200410085792 A CN200410085792 A CN 200410085792A CN 100441586 C CN100441586 C CN 100441586C
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- 150000004696 coordination complex Chemical class 0.000 title 2
- 125000003118 aryl group Chemical group 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 5
- 125000002524 organometallic group Chemical group 0.000 claims description 21
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 9
- -1 methoxyl group Chemical group 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 150000001721 carbon Chemical group 0.000 claims description 5
- 229910052723 transition metal Inorganic materials 0.000 claims description 5
- 150000003624 transition metals Chemical class 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 3
- 229910052762 osmium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims 2
- 239000003446 ligand Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- VLRICFVOGGIMKK-UHFFFAOYSA-N pyrazol-1-yloxyboronic acid Chemical compound OB(O)ON1C=CC=N1 VLRICFVOGGIMKK-UHFFFAOYSA-N 0.000 abstract description 6
- 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 abstract description 4
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 abstract 4
- 125000001072 heteroaryl group Chemical group 0.000 abstract 4
- 125000000753 cycloalkyl group Chemical group 0.000 abstract 3
- 125000004404 heteroalkyl group Chemical group 0.000 abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 238000005401 electroluminescence Methods 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 4
- 125000006575 electron-withdrawing group Chemical group 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 150000003217 pyrazoles Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 239000004328 sodium tetraborate Substances 0.000 description 2
- 235000010339 sodium tetraborate Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- RAAGZOYMEQDCTD-UHFFFAOYSA-N 2-fluorobenzoyl chloride Chemical class FC1=CC=CC=C1C(Cl)=O RAAGZOYMEQDCTD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical group CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 238000011175 product filtration Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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Abstract
The present invention relates to a complex compound with an imidazole ring ligand and a tetrakis (1-pyrazolyl) borate or bispyrazolyl ligand, which has photoluminescent property, and can be applied to an organic electroluminescence device. The present invention has the chemical formula (I) or (II), wherein M is transitional metal, R<1> is H, halogen atoms, C<1-18> alkyl, C<1-18> alkoxyl, C<3-18> hetero-alkyl, C<3-20> aromatic groups, C<3-20> hetero-aromatic groups, or C<3-20> cycloalkyl, R<2>s are same or different, each R<2> is H, C<1-18> alkyl, C<1-18> alkoxyl, C<3-18> hetero-alkyl, C<3-20> aromatic groups, C<3-20> hetero-aromatic groups, or C<3-20> cycloalkyl, or two R<2>s connected together, and carbon atoms connected with the two R<2>s jointly form an aromatic ring or a hetero-aromatic ring with 4 to 14 members; R<3>s are same or different, each R<3> is H, CN, tricyanovinyl, halogen, CX3, C<1-18> alkyl, C<1-18> alkoxyl, C<3-18> hetero-alkyl, C<3-20> aromatic groups, C<3-20> hetero-aromatic groups or C<3-20> cycloalkyl, wherein X is halogen; each R<4> is H, C<1-3> alkyl, C<1-3> alkoxyl or C<1-3> alkyl substituted by halogen (F, Cl, Br).
Description
Technical field that the present invention belongs to
The relevant a kind of organometallic complex that is used for Organnic electroluminescent device of the present invention is particularly to a kind of organometallic complex, and it can be used as the organic light emitting medium layer of Organnic electroluminescent device.
Prior art
Organnic electroluminescent device also is called Organic Light Emitting Diode (OLED), is with a kind of photodiode (LED) of organic layer as active coating.Because Organnic electroluminescent device has advantages such as low voltage operating, high brightness, in light weight, wide viewing angle and high correlative value, is used on the flat panel display gradually in recent years.
Generally speaking, OLED comprises pair of electrodes, and the organic light emitting medium layer between electrode.Luminous is to lead because of in following phenomenon.When electric field imposed on two electrodes, negative electrode penetrated electronics to the organic light emitting medium layer, and anode penetrates electric cave to the organic light emitting medium layer.When electronics combines in the organic light emitting medium layer with electric cave, can produce exciton.The combination again in electronics and electric cave just is accompanied by luminous.
According to electric cave and electronic spin attitude, the exciton that is produced by the combination of electric cave and electronics can have the spin state of triplet state or singlet state.Luminously by the singlet state exciton produced be fluorescent, and luminously by triplet exciton produced be phosphorescence.The luminous efficiency of phosphorescence is three times of fluorescent.Therefore, developing high efficiency phosphor material is very important with the luminous efficiency of promoting OLED.
More existing organometallic complexs are reported out have very strong phosphorescence (Lamansky, et al., Inorganic Chemistry, 2001,40,1704), and utilize these complex compounds to make effective OLED, luminous (Lamansky in green arrives red scope, et al., J.Am.Chem.Soc., 2001,123,4304).U.S. patent application case discloses the organometallic complex that discloses a kind of phosphorescence in 20030072964A1 number, and it comprises phenylquinoline acid group ligand.U.S. patent application case discloses 20020024293A1,20020182441A1,20030116788A1 and 20040102632A1 number, and other luminous organometallic complexs of exposure are also arranged.United States Patent (USP) the 6th, 687, disclose a kind of luminescent material, have following ligand for No. 266:
Or have following array structure:
It discloses the preferable example of X is methyl ethyl diketone acid group (acetylacetonate; Acac), pyridine carboxylic acid root (picolinate; Pic), reach dipivaloylmetanate (tributyl acac; T-butyl acac), all have ketone group (=O), as auxiliary ligand (ancillary ligand).Perhaps another embodiment is 3 for m, and n is 0.
Yet,, still have sizable growth requirement for the organometallic complex of green light.
Summary of the invention
The invention provides a kind of organometallic complex, have following chemical formula (I) or (II):
Wherein,
M is a transition metal;
R
1Be H, halogen atom, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl;
Each R
2For identical or different, and be H, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, perhaps two R
2Link together and with common aromatic nucleus or the assorted aromatic nucleus that forms 4 to 14 Yuans of its carbon atom that is connected;
Each R
3For identical or different, and be H, CN, three acrylonitrile bases (tricyanovinyl), halogen, CX
3, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, wherein X is a halogen; And
Each R
4Be H, C
1-3Alkyl, C
1-3Alkoxyl group or the C that replaces through halogen (F, Cl, Br)
1-3Alkyl.
The present invention provides a kind of Organnic electroluminescent device again, and it comprises pair of electrodes, and the organic light emitting medium layer between this counter electrode, and wherein this organic light emitting medium layer comprises just like above-mentioned organometallic complex.
Embodiment
The invention provides a kind of organometallic complex that contains imidazoles ligand (imidazole ligand) and four pyrazoles boron or double pyrazole ligand, have chemical formula (I) or (II):
At chemical formula (I) or (II), M is a transition metal, preferably has d
6The transition metal of electronics orbital, such as but not limited to: Ir, Pt, Os, Re, Ru, or Rh are preferably Ir.
R
1Be H, halogen atom, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl.Preferable situation is R
1For pushing away electronics base (electron-donatinggroup), for example C
1-18Alkyl, C
1-18Alkoxyl group, or C
3-18Assorted alkyl.The representative example that pushes away the electronics base comprises methyl, methoxyl group, cyclohexyl.In particular embodiments of the invention, work as R
1For pushing away electronics base when methyl or phenyl (for example), blue displacement (blue shift) can take place in maximum emission wavelength.
Each R
2For identical or different, and be H, C independently
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl.Preferable situation is R
2For pushing away the electronics base, also can cause blue displacement.Representative example comprises methyl, isobutyl-, and methoxyl group.Perhaps, two R
2Link together and with common aromatic nucleus or the assorted aromatic nucleus that forms 4 to 14 Yuans of its carbon atom that is connected.In particular embodiments of the invention, two R
2Link together and with the common phenyl ring that forms of its carbon atom that is connected.Other object lessons of 4 to 14 Yuans aromatic nucleus comprise naphthalene and phenanthrene.In addition, in other specific embodiments of the present invention, these two R
2Be not to be connected individually.
Each R
3For identical or different, and be H, CN, three acrylonitrile bases, halogen, CX independently
3, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, wherein X is a halogen.Preferable situation is R
3Be electron withdrawing group, for example halogen, CN, three acrylonitrile bases, or CX
3, wherein X is a halogen.The electron withdrawing group that is fit to comprises F, CF
3, CN and three acrylonitrile bases.In particular embodiments of the invention, work as R
3During for electron withdrawing group (as F), maximum emission wavelength can produce blue displacement.
Each R
4Be H, C
1-3Alkyl, C
1-3Alkoxyl group or the C that replaces through halogen (F, Cl, Br)
1-3Alkyl.
List particular instance down according to organometallic complex of the present invention:
In above-claimed cpd, R
2Be to be identical or different methyl, isobutyl-or methoxyl group.
Organometallic complex of the present invention can be luminous, particularly is green-emitting phosphorescence in several object lessons, or can be as green light filler (dopant) material, can be used in the luminescence medium layer of OLED for example.For example, be used in the luminescent layer of organic light emitting medium layer or further in the luminescent layer of organic light emitting medium layer as green glow filler material.This kind luminescent material novelty belongs to higher photoluminescence efficiency person in the green light material.
Below by several embodiment to illustrate further the features and advantages of the present invention.
Example
Embodiment 1
Synthetic two [1,2-phenylbenzene-1H-benzoglyoxaline] (four (1-pyrazoles) boric acid) iridium (III) (compound 1) route of synthesis is as follows:
Step 1: with N-phenyl-1, (7.36g after 40mmol) 40ml adds the 250ml round-bottomed bottle, adds triethylamine 10ml to the 2-phenylenediamine, is cooled to 0 ℃.Other gets Benzoyl chloride, and (5.6g 40mmol) behind the dichloromethane solution of adding 40ml, slowly injects the 250ml round-bottomed bottle again, and reacted 6 hours under nitrogen environment.Reaction finishes have precipitation to separate out after the back adds ether.After solid product filter collected, with ether flushing solid several times, at last with solid product with the decompression type of heating, the dehydration back forms final product: 1,2-phenylbenzene-1H-benzoglyoxaline, productive rate are 7.56g, 70%.
Step 2: with 1,2-phenylbenzene-1H-benzoglyoxaline (6.75g, 25mmol) with iridium chloride (III) trihydrate (4.2g, 12mmol) behind the adding 250ml round-bottomed bottle, the mixing solutions that adds 60ml ethoxy ethanol and 20ml water, reflux is 12 hours under nitrogen, has yellow mercury oxide to generate after the cooling.With deionized water and hexane flushing throw out for several times, can get the iridochloride bridge joint dipolymer (Iridiumdichloro-bridged dimer) (7.35g, 4.8mmol).
Step 3: with the dipolymer (7.35g of above-mentioned iridochloride bridge joint, 4.8mmol) and four (1-pyrazoles) Sodium Tetraborate (sodium tetrakis (1-pyrazolyl) borate) (3.02g, 10mmol) be dissolved in the ethoxy ethanol, and after reacting 12 hours under the room temperature, can get product two [1,2-phenylbenzene-1H-benzoglyoxaline] (four (1-pyrazoles) boric acid) iridium (III) (5.04g, 5mmol) (compound 1).Final product be with continuous subliming method in addition purifying it.
Embodiment 2
Synthetic two [2-(2,4 difluorobenzene base)-1-phenyl-1H-benzoglyoxaline] (four (1-pyrazoles) boric acid) iridium (III) (compound (2)
Step 1: with N-phenyl-1, the 2-phenylenediamine (1.84g, 10mmol) add the 250ml round-bottomed bottle with the 40ml methylene dichloride after, add triethylamine 30ml, be cooled to 0 ℃.Other gets 2, and (1.94g 11mmol) behind the dichloromethane solution of adding 40ml, slowly injects the 250ml round-bottomed bottle, and reacted 6 hours under nitrogen environment 4-two fluoro-Benzoyl chlorides again.Reacting end back adding ether has precipitation to separate out, after solid product filtration collection, with ether flushing solid several times, at last with solid product with the decompression type of heating, dehydration back forms final product: 2-(2,4 difluorobenzene base)-1-phenyl-1H-benzoglyoxaline, productive rate is 1.83g, 60%.
Step 2: with 2-(2, the 4-difluorophenyl)-1-phenyl-1H-benzoglyoxaline (1.83g, 6mmol) with iridium chloride (III) trihydrate (1.1g, 3mmol) behind the adding 250ml round-bottomed bottle, the mixing solutions that adds 30ml ethoxy ethanol and 10ml water, reflux is 12 hours under nitrogen, has yellow mercury oxide to generate after the cooling.With deionized water and hexane flushing throw out for several times, can get the iridochloride bridge joint dipolymer (2.01g, 1.2mmol).
Step 3: with the dipolymer (2.01g of above-mentioned iridochloride bridge joint, 1.2mmol) and four (1-pyrazoles) Sodium Tetraborate (sodium tetrakis (1-pyrazolyl) borate) (0.91g, 3mmol) be dissolved in the ethoxy ethanol, and after reacting 12 hours under the room temperature, can getting product, two [2-(2, the 4-difluorophenyl)-1-phenyl-1H-benzoglyoxaline (four (1-pyrazolyl) boric acid) iridium (III) (1.08g, 1mmol) (compound 2).Final product be with continuous subliming method in addition purifying it.
Embodiment 3
Synthetic (III) two [1,2-phenylbenzene-1H-benzoglyoxaline] (two (1-pyrazoles) boric acid) iridium
As embodiment 1 described synthesis step, carry out but replace four (1-pyrazolyl) Sodium Tetraborate (sodium tetrakis (1-pyrazolyl) borate) with yellow soda ash (10mmol) and pyrazoles (10mmol), obtain the alleged compound of title.
Embodiment 4
Synthetic (III) two [2-(2,4 difluorobenzene base)-1-phenyl-1H-benzoglyoxaline] (two (1-pyrazolyl) boric acid) iridium
As embodiment 2 described synthesis steps, carry out but replace four (1-pyrazolyl) Sodium Tetraborate with yellow soda ash (3mmol) and pyrazoles (3mmol), obtain the alleged compound of title.
Fig. 1 show compound (1) and (2) under different wave length at CH
2Cl
2The fluorescence spectra that records in the solution.For compound (1), with imidazole ring and phenyl ring that Ir is connected on, do not have substituting group, measured maximum emission wavelength is 515nm.When phenyl ring with imidazole ring contraposition and adjacent position on when having F (electron withdrawing group) to replace (as compound 2), have blue displacement and take place, wavelength shift is to 506nm.
Though the present invention discloses as above with preferred embodiment, so it is not in order to limit the present invention.Anyly be familiar with this skill person, without departing from the spirit and scope of the present invention, when doing a little change and retouching.Therefore protection scope of the present invention is when looking the accompanying Claim book.
Brief description of drawingsfig
Fig. 1 shows compound (1) and (2) figure in photoluminescence (PL) intensity of different wave length.
Claims (10)
1. organometallic complex has following chemical formula (I) or (II):
Wherein,
M is a transition metal;
R
1Be H, halogen atom, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl;
Each R
2For identical or different, and be H, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, perhaps two R
2Link together and with common aromatic nucleus or the assorted aromatic nucleus that forms 4 to 14 yuan of its carbon atom that is connected;
Each R
3For identical or different, and be H, CN, three acrylonitrile bases, halogen, CX
3, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, wherein X is a halogen; And
Each R
4Be H, C
1-3Alkyl, C
1-3Alkoxyl group or the C that replaces through halogen
1-3Alkyl.
2. organometallic complex as claimed in claim 1, wherein each R
4Be the C that replaces through F, Cl, Br
1-3Alkyl.
3. organometallic complex as claimed in claim 1, wherein M is Ir, Pt, Os, Re, Ru or Rh.
4. organometallic complex as claimed in claim 1, it has one of following chemical formula:
Wherein, R
2Be identical or different methyl, isobutyl-or methoxyl group.
5. organometallic complex as claimed in claim 1, it is a luminescent material.
6. organometallic complex as claimed in claim 1, it is a green phosphorescent filler material.
7. Organnic electroluminescent device, it comprises pair of electrodes, and the organic light emitting medium layer between this counter electrode,
Wherein this organic light emitting medium layer comprises an organometallic complex, has chemical formula (I) or (II):
Wherein,
M is a transition metal;
R
1Be H, halogen atom, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl;
Each R
2For identical or different, and be H, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, perhaps two R
2Be connected together and with common aromatic nucleus or the assorted aromatic nucleus that forms 4 to 14 yuan of its carbon atom that is connected;
Each R
3For identical or different, and be H, CN, three acrylonitrile bases, halogen, CX
3, C
1-18Alkyl, C
1-18Alkoxyl group, C
3-18Assorted alkyl, C
3-20Aromatic base, C
3-20Assorted aromatic base or C
3-20Cycloalkyl, wherein X is a halogen; And
Each R
4Be H, C
1-3Alkyl, C
1-3Alkoxyl group or the C that replaces through halogen
1-3Alkyl.
8. Organnic electroluminescent device as claimed in claim 7, wherein each R
4Be the C that replaces through F, Cl, Br
1-3Alkyl.
9. Organnic electroluminescent device as claimed in claim 7, wherein M is Ir, Pt, Os, Re, Ru or Rh.
10. Organnic electroluminescent device as claimed in claim 7, wherein this organometallic complex has one of following chemical formula:
Wherein, R
2Be identical or different methyl, isobutyl-or methoxyl group.
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| CN100358971C (en) * | 2005-10-11 | 2008-01-02 | 友达光电股份有限公司 | Organic light-emitting material and organic light-emitting device |
| DE102008048336A1 (en) | 2008-09-22 | 2010-03-25 | Merck Patent Gmbh | Mononuclear neutral copper (I) complexes and their use for the production of optoelectronic devices |
| CN102675373B (en) * | 2012-04-06 | 2014-08-27 | 华中师范大学 | Methanol indicator and preparation method thereof |
| CN102731404B (en) * | 2012-07-19 | 2014-06-11 | 河南大学 | Double-pyrazole ring compound and derivative, preparation method and application thereof |
| GB2533268A (en) * | 2014-12-02 | 2016-06-22 | Cambridge Display Tech Ltd | Organic light-emitting device |
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| US20030072964A1 (en) * | 2001-10-17 | 2003-04-17 | Kwong Raymond C. | Phosphorescent compounds and devices comprising the same |
| US20030116788A1 (en) * | 2001-11-09 | 2003-06-26 | Jsr Corporation | Light emitting polymer composition, and organic electroluminescence device and production process thereof |
| CN1454448A (en) * | 2000-08-11 | 2003-11-05 | 普林斯顿大学理事会 | Organometallic compounds and emission-shifting organic electrophosphorescence |
| CN1478372A (en) * | 2000-11-30 | 2004-02-25 | ������������ʽ���� | Luminescent element and display |
| WO2004017043A2 (en) * | 2002-08-16 | 2004-02-26 | The University Of Southern California | Organic light emitting materials with anionic ligand |
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| CN1513045A (en) * | 2001-04-13 | 2004-07-14 | ��ʽ����뵼����Դ�о��� | Organic light-emitting device and light-emitting apparatus comprising the device |
| CN1538986A (en) * | 2001-09-04 | 2004-10-20 | ������������ʽ���� | High-molecular compounds and organic luminescent devices |
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| CN1454448A (en) * | 2000-08-11 | 2003-11-05 | 普林斯顿大学理事会 | Organometallic compounds and emission-shifting organic electrophosphorescence |
| CN1478372A (en) * | 2000-11-30 | 2004-02-25 | ������������ʽ���� | Luminescent element and display |
| CN1500093A (en) * | 2001-04-05 | 2004-05-26 | �����л��뵼������˾ | Rhodium and iridium complexes |
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| WO2004017043A2 (en) * | 2002-08-16 | 2004-02-26 | The University Of Southern California | Organic light emitting materials with anionic ligand |
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