CN102887922B - A kind of synthetic method of iridium compounds - Google Patents
A kind of synthetic method of iridium compounds Download PDFInfo
- Publication number
- CN102887922B CN102887922B CN201210353282.4A CN201210353282A CN102887922B CN 102887922 B CN102887922 B CN 102887922B CN 201210353282 A CN201210353282 A CN 201210353282A CN 102887922 B CN102887922 B CN 102887922B
- Authority
- CN
- China
- Prior art keywords
- reaction
- water
- iridium
- synthetic method
- add
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- 150000002504 iridium compounds Chemical class 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 9
- 230000026030 halogenation Effects 0.000 claims abstract description 8
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 8
- HUGYAFGADWVRIN-UHFFFAOYSA-N iridium;hydrate Chemical compound O.[Ir] HUGYAFGADWVRIN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 claims description 3
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
- UOHBMRODJBFDPN-UHFFFAOYSA-N C(C)(C)(C)O.[Li] Chemical compound C(C)(C)(C)O.[Li] UOHBMRODJBFDPN-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 claims description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 2
- CCZVEWRRAVASGL-UHFFFAOYSA-N lithium;2-methanidylpropane Chemical compound [Li+].CC(C)[CH2-] CCZVEWRRAVASGL-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- LMHHRCOWPQNFTF-UHFFFAOYSA-N s-propan-2-yl azepane-1-carbothioate Chemical compound CC(C)SC(=O)N1CCCCCC1 LMHHRCOWPQNFTF-UHFFFAOYSA-N 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- KBXXFKPVKJZGJG-UHFFFAOYSA-K tribromoiridium;hydrate Chemical compound O.Br[Ir](Br)Br KBXXFKPVKJZGJG-UHFFFAOYSA-K 0.000 claims description 2
- 239000007787 solid Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 229910052741 iridium Inorganic materials 0.000 description 9
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- FSEXLNMNADBYJU-UHFFFAOYSA-N 2-phenylquinoline Chemical compound C1=CC=CC=C1C1=CC=C(C=CC=C2)C2=N1 FSEXLNMNADBYJU-UHFFFAOYSA-N 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 6
- 230000005281 excited state Effects 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 150000002503 iridium Chemical class 0.000 description 4
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 150000002085 enols Chemical group 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-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
- 239000003513 alkali Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- -1 alcohols sodium salt Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001979 organolithium group Chemical group 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N propylene glycol Substances CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention provides a kind of synthetic method of organic-metallic iridium compound, comprise: (1) three halogenation iridium hydrate A and neutral ligand B reacts, generate the iridic compound of band halo bridge: L2Ir (μ-X) 2IrL2, L: represent the two coordination annular metal parts formed by neutral ligand, (μ-X): represent a bridge like halogen, the iridic compound of (2) band halo bridge is obtained by reacting with part C excessive a little
lX represents another part formed by part C; It is characterized in that, the reaction of the described the first step comprises the steps: three halogenation iridium hydrate A, neutral ligand B adds in water-miscible organic solvent, water, back flow reaction a few hours, coldly to go, is poured into water, filtration product, obtains the iridic compound being with halo bridge: L2Ir (μ-X) 2IrL2.
Description
Technical field
The present invention relates to the synthesis of the iridium class material in luminous organic material, particularly to the synthesis of iridium class red light material, mainly to the improvement of traditional method, the method for improvement improves yield, shortens the reaction times, is conducive to the popularization of iridium class material.
Background technology
In recent years, extensive research and development had been carried out to organic electroluminescence device.In the basic structure of this luminous element, the layer containing luminophore is inserted between pair of electrodes, by applying voltage on this element, can obtain the light emission of self-luminescent material.
Because this luminous element is self-emission device, therefore they have advantage with saving in backlight demand in high pixel visibility relative to liquid-crystal display, are such as regarded as thus being suitable for flat panel displaying element.Luminous element is ceiling advantage equally, because they are thin and lightweight.Response very is at a high speed one of feature of this element.
In addition, due to this luminous element can be formed in the form of a film, therefore planar light emission can be provided.Therefore, easily can be formed there is large-area element.This is be difficult to adopt with incandescent light and the LED pointolite that is representative or take luminescent lamp as the feature that the linear light sorurce of representative obtains.Therefore, luminous element also has large potentiality as the planar light source etc. that can be applicable to throw light on.
The excited state formed by organic compound can be singlet or triplet state.From singlet excited state (S
*) transmitting be fluorescence, and from triplet excited states (T
*) transmitting be called as phosphorescence.In addition, think that in luminous element, it adds up generation than being S
*: T
*=1: 3.Being in photoemissive compound by the energy conversion of singlet excited state, at room temperature not observing the transmitting from triplet excited states, and only observing the transmitting from singlet excited state.Therefore, think and the theoretical limit using the interior two word efficiency of the luminous element of fluorescent chemicals to have 25% be based upon the S of 1: 3
*with T
*ratio.Therefore organic electromechanical phosphorescent material is the class material recently attracted attention, there is high luminous efficiency and the electroluminescent organic material of luminosity, it is by introducing the method for heavy metal atom, originally the triplet transition prohibited under make use of room temperature, thus enable internal quantum theory reach 100%, be single fluorescent material 4 times (1, CaoY., Parker I.D., Heeger J., Nature, 1999,397:414-417.2, Wohlgenann M., etal.Nature, 2001,409:494-497.).The heavy metal atom that organic electromechanical phosphorescent material is conventional mostly is transition metal, wherein with iridium most widely used, research is the most detailed, this is because the phosphorescent emissions stronger under having high efficiency, room temperature of metal iridium complex and emission wavelength can be regulated by the adjustment of ligand structure to make the color of electroluminescent device cover whole visible region.Therefore the efficient metal iridium complex of design studies synthesizing new, splits phosphorescing materia and is significant.
As the display of OLED tri-look, red light material is that application is maximum, and mainly quinoline, isoquinoline 99.9, pyrazine are main, and wherein methyl ethyl diketone and derivative thereof account for significant proportion, and three identical part iridium class materials synthesis are also changed by methyl ethyl diketone intermediate.Synthetic method mainly ethylene glycol monomethyl ether or methyl ether, the salt of wormwood reaction 24-48 hour of current bibliographical information.The problems such as this method long reaction time, yield is low, side reaction is many.
Summary of the invention
For ruddiness at synthesis of acetyl acetone class ruddiness Problems existing, the present inventor has carefully analyzed dissimilar red light material, analyzes red light material reaction mechanism, proposes improvement project.Reaction is that methyl ethyl diketone loses proton, changes enol form into by under alkali effect, then reacts with chlorine bridge, obtains red light material; Wherein methyl ethyl diketone and carbonate reaction are that out-phase is reacted, and determine the speed of whole reaction.Chlorine bridge can change solution into solvent molecule generation coordination in acetone, ethanol, methyl alcohol equal solvent, and the enol form of methyl ethyl diketone can react with it rapidly, obtains red light material.Traditional method synthesis under out-phase, hot conditions react (more than 130 degree), methyl ethyl diketone and carbonate reaction slow, chlorine bridge is more stable, also determines speed of response, and yield is lower.Such as Pyrazine (the CN101270133 of Japanese Semiconductor Co., Ltd report, CN102190653, because ligand reaction is more weak, traditional method cannot obtain high yield product (10-20%), need under ul-trasonic irradiation, be therefore not suitable for industrial application.Solve the problems such as productive rate is low, long reaction time, need to solve from chlorine bridge and methyl ethyl diketone two methods, chlorine bridge can dissociate, and forms ligand molecule with solvent molecule, and selective solvent will can form ligand molecule with chlorine bridge; The alkali selected can be homogeneous phase with solvent, does not produce side reaction, promotes the generation (II) of enol form, improves speed of response.The present inventor improves prior synthesizing method on the basis of great many of experiments.
The synthetic method of organic-metallic iridium compound, comprise two steps independently to react: (1) three halogenation iridium hydrate A and neutral ligand B reacts, generate the iridic compound of band halo bridge: L2Ir (μ-X) 2IrL2, L: represent the two coordination annular metal parts formed by neutral ligand, (μ-X): represent a bridge like halogen, the iridic compound of (2) band halo bridge is obtained by reacting with part C excessive a little
lX represents another part formed by part C; It is characterized in that: described the first step reaction comprises the steps:, three halogenation iridium hydrates, neutral ligand add in water-miscible organic solvent, water, back flow reaction a few hours, coldly to go, be poured into water, certain inorganic salt are added in water, filtration product, obtains the iridic compound being with halo bridge: L2Ir (μ-X) 2IrL2.
1, described water-miscible organic solvent M is cellosolvo, 2-methyl cellosolve, 1,3-PD, 1,2-PD, the water-soluble alcohol such as ethylene glycol or glycerol; The volume ratio of described water-miscible organic solvent and water is arbitrary proportion.Reaction terminates, and adds certain inorganic salt, as long as the water miscible inorganic salt of Inorganic Salts, have no particular limits in water; Inorganic salt add the purifying and aftertreatment that are conducive to product, particularly large to solubleness product is one and well selects.
2, described three halogenation iridium hydrates are iridous chloride hydrate, tribromide iridium hydrate.
3, described second step reaction comprises the steps: that part C, L2Ir (μ-X) 2IrL2 adds in solvent N, adds proper catalyst X, at a certain temperature stirred for several hour, product separation.
Second step reaction part C can be structural formula below:
A1 ~ 6:H, methyl, ethyl, propyl group, sec.-propyl, F, CF
3, phenyl; A1 ~ 6 can be identical or different.
4, catalyzer X is the one in organic bases, and suitable organic bases dissolves each other with solvent N, causes part C and L2Ir (μ-X) 2IrL2 to react rapidly.The temperature of reaction that adds of catalyzer X can from-78 DEG C ~ 110 DEG C, and preferred scope is-50 DEG C ~ 110 DEG C, and more excellent scope is-50 DEG C ~ 100 DEG C.Reaction times can 30 minutes to 10 hours, and the more excellent time can 30 minutes to 6 hours.Reaction terminates direct filtration, and the product purity 99% obtained, can reach industrial application requirement.
5, the add-on of catalyzer X is 1% ~ 10 times of L2Ir (μ-X) 2IrL2, and preferred scope is 5% ~ 10 times, and more excellent scope is 5% ~ 8 times.The add-on of part C be L2Ir (μ-X) 2IrL2 from 2 ~ 20 times, optimization range is from 2 ~ 15 times, and more optimization range is from 2 ~ 10 times.
6, according to claim 5, catalyzer X can be:
(1) alcohols sodium salt, the sylvite such as sodium tert-butoxide, sodium tert-butoxide, trimethyl carbinol lithium, sodium methylate, sodium ethylate, sodium isopropylate.
(2) organic amine such as methylamine, dimethylamine, ethamine, diethylamine, triethylamine, Tributylamine.
(3) the organolithium class such as lithium methide, n-Butyl Lithium, isobutyl-lithium, tert-butyl lithium.
7, the second solvent N: can be the mixture of one or more that methyl alcohol, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol, acetone, butanone, THF, ether, propyl ether etc. contribute in alcohols that chlorine bridge dissociates or ether solvent, temperature controls at-78 DEG C ~ 110 DEG C.
By the present inventor's great many of experiments, find that the method improved is applicable to the synthesis of ruddiness, substantially reduce the reaction times, improve yield; The more important thing is, reaction terminates direct filtration to obtain desired product, does not need purifying just can obtain the high purity ruddiness of more than 99%, provides cost savings, be conducive to the popularization of red light material.
Accompanying drawing explanation
Fig. 1 is iridium, two [the fluoro-2-of 5-(1-isoquinoline 99.9)-4-aminomethyl phenyl (2,4-diacetylmethane)-nuclear magnetic spectrogram, except product peak is reaction solvent and trace part peak.
Fig. 2 is two (2-phenylquinoline) (methyl ethyl diketone) iridium (III) (Ir (2-phq) 2 (acac)).
Fig. 3 is two (2-phenylquinolines) (2,2,6,6-tetramethyl-heptane-3,5-ketone) iridium (III) (Ir (dpm) PQ2).
Fig. 4 is iridium, two (5-bis-[f, h] pyrazine-) (methyl ethyl diketones)-and, is solvent and micro-part peak except product peak.
Fig. 5 is iridium, two [2-(3,5-phenylbenzene-2-pyrazine-N1) phenyl-] (2,2,6,6-tetramethyl-1-3,5-heptane diketone)-and, is reaction solvent and micro-part peak except product peak.
Embodiment
The invention provides a kind of ruddiness preparation method of improvement, for making object of the present invention, technical scheme, effect more clear, complete, is below to further description of the present invention.The embodiment that should be appreciated that herein is only used for explaining the present invention, does not limit the present invention, all meet the scope of the invention all within protection.
Embodiment 1, iridium, two [the fluoro-2-of 5-(1-isoquinoline 99.9)-4-aminomethyl phenyl (2,4-diacetylmethane)-synthesis
500ML four-hole bottle adds 1.5G hydrated iridium trichloride A, 4G part B1 (reference Dalton Trans., 2005,1583-1590), 200ML ethylene glycol ethyl ether, 50ML water successively.Fill nitrogen 30 minutes, heated overnight at reflux.2L water, 200G lithium chloride stirring and dissolving, be poured into water reaction soln, separate out a large amount of red solid, filters, and dries and obtain 2.6G red solid powder, yield 90%.
3L four-hole bottle adds W125G, methyl ethyl diketone (C1) 8G, sodium methylate 20G, 2L methyl alcohol successively, inflated with nitrogen stirs 30 minutes, temperature rising reflux (64 degree) 2 hours, obtain red solid bright-coloured in a large number, filter, methyl alcohol 200ML washs, oven dry obtains 27G red solid, yield 95%.HNMR is shown in accompanying drawing.
The synthesis of embodiment 2, two (2-phenylquinoline) (methyl ethyl diketone) iridium (III) (Ir (2-phq) 2 (acac))
3L four-hole bottle adds 25G hydrated iridium trichloride A, 37G part B2 (reference Dalton Trans., 2005,1583-1590), 1500ML ethylene glycol, 500ML water successively.Fill nitrogen 30 minutes, heated overnight at reflux, obtains red solid.5L water, 1KG Repone K stirring and dissolving, be poured into water reaction soln, separate out a large amount of solid, filters, and dries and obtain 45G red solid powder, yield 92%.
3L four-hole bottle adds W2 25G, methyl ethyl diketone (C1) 8G, dimethylamine 20G, 2L methyl alcohol successively, inflated with nitrogen stirs 30 minutes, temperature rising reflux (64 degree) 2 hours, obtain red solid bright-coloured in a large number, filter, methyl alcohol 200ML washs, oven dry obtains 27G red solid, yield 94%.HNMR is shown in accompanying drawing.
Embodiment 3, two (2-phenylquinoline) (2,2,6,6-tetramethyl-heptane-3,5-ketone) iridium (III) (Ir (dpm) PQ2)
500ML four-hole bottle adds 1.5G hydrated iridium trichloride A, 4G part B3 (reference Dalton Trans., 2005,1583-1590), 200ML glycerol, 100ML water successively.Fill nitrogen 30 minutes, heated overnight at reflux.2L water, 200G lithium chloride stirring and dissolving, be poured into water reaction soln, separate out a large amount of solid, filters, and dries and obtain 2.6G red solid powder, yield 90%.
3L four-hole bottle adds W3 25G, 2 successively, 2,6,6-tetramethyl-heptane-3,5-ketone (C2) 15G, diethylamine 20G, 2L methyl alcohol, ethanol (1: 1), inflated with nitrogen stirs 30 minutes, temperature rising reflux 1 hour, obtain red solid bright-coloured in a large number, filter, methyl alcohol 200ML washs, oven dry obtains 28G red solid, yield 95%.HNMR is shown in accompanying drawing.
Embodiment 4, iridium, two (5-bis-[f, h] pyrazine-) (methyl ethyl diketones)-
500ML four-hole bottle adds 1.5G hydrated iridium trichloride A, 4G part B4 (reference Dalton Trans., 2005,1583-1590, US7696348), 200ML ethylene glycol monomethyl ether, 50ML water successively.Fill nitrogen 30 minutes, heated overnight at reflux, obtains red solid.2L water, 200G lithium chloride stirring and dissolving, be poured into water reaction soln, separate out a large amount of solid, filters, and dries and obtain 2.5G red solid powder, yield 90%.
3L four-hole bottle adds W4 25G, methyl ethyl diketone (C1) 15G, Tributylamine 20G, 2L methyl alcohol, ethanol (1: 1) successively, inflated with nitrogen stirs 30 minutes, temperature rising reflux 2 hours, obtain red solid bright-coloured in a large number, filter, methyl alcohol 200ML washs, oven dry obtains 26G red solid, yield 90%.(document Adv.Mater.2003,15,224-228 report 70%, 12 hours reaction times.)
Embodiment 5, iridium, two [2-(3,5-phenylbenzene-2-pyrazine-N1) phenyl-] (2,2,6,6-tetramethyl-1-3,5-heptane diketone)-
500ML four-hole bottle adds 1.5G hydrated iridium trichloride A, 4G part B5 (reference US7696348), 200ML1,2-propylene glycol, 50ML water successively.Fill nitrogen 30 minutes, heated overnight at reflux, obtains red solid.2L water, 200G sodium-chlor stirring and dissolving, be poured into water reaction soln, separate out a large amount of solid, filters, and dries and obtain 2.6G red solid powder, yield 90%.
3L four-hole bottle adds W525G, 2 successively, 2,6,6-tetramethyl-heptane-3,5-ketone (C2) 15G, 2LTHF, inflated with nitrogen stirs 30 minutes, and-20 degree drip lithium methide 30ML (2.5mol/l, diethyl ether solution), react 2 hours, obtain red solid bright-coloured in a large number, filter, methyl alcohol 200ML washs, oven dry obtains 28G red solid, yield 95%.HNMR is shown in accompanying drawing.
Claims (7)
1. the synthetic method of red organic-metallic iridium compound, comprises two steps and independently reacts: (1) three halogenation iridium hydrate A and neutral ligand B reacts, and generates the iridic compound of band halo bridge: L
2ir (μ-X)
2irL
2, L: represent the two coordination annular metal parts formed by neutral ligand, (μ-X): represent a bridge like halogen, the iridic compound of (2) band halo bridge is obtained by reacting [C ︵ N] with part C excessive a little
2(LX); LX represents another part formed by part C; It is characterized in that, the reaction of the described the first step comprises the steps: three halogenation iridium hydrate A, neutral ligand B adds in water-miscible organic solvent, water, back flow reaction a few hours, cool, be poured into water, in water, add certain inorganic salt, filtration product, obtain the iridic compound being with halo bridge: L
2ir (μ-X)
2irL
2, Inorganic Salts is water miscible inorganic salt, inorganic salt add the purifying and aftertreatment that are conducive to product, wherein said organic-metallic iridium compound is red light material,
Described second step reaction comprises the steps: part C, L
2ir (μ-X)
2irL
2add in solvent N, add proper catalyst X, at a certain temperature stirred for several hour, product separation,
Wherein catalyzer X is the one in organic bases, and suitable organic bases dissolves each other with solvent N, causes part C and L2Ir (μ-X) 2IrL2 to react rapidly, does not cause other side reaction; The temperature of reaction that adds of catalyzer X is from-78 DEG C ~ 110 DEG C; Reaction times is 30 minutes to 10 hours;
Wherein catalyzer X is selected from:
(1) sodium tert-butoxide, sodium tert-butoxide, trimethyl carbinol lithium, sodium methylate, sodium ethylate, sodium isopropylate;
(2) methylamine, dimethylamine, ethamine, diethylamine, triethylamine, Tributylamine; Or
(3) lithium methide, n-Butyl Lithium, isobutyl-lithium, tert-butyl lithium,
Described solvent N is the mixture of one or more in methyl alcohol, ethanol, Virahol, isopropylcarbinol, the trimethyl carbinol, acetone, butanone, THF, ether, propyl ether, and temperature controls at-78 DEG C ~ 110 DEG C;
Described second step reaction part C is structural formula below:
A1 ~ 6:H, methyl, ethyl, propyl group, sec.-propyl, F, CF
3, phenyl; A1 ~ 6 are identical or different.
2. synthetic method according to claim 1, described water-miscible organic solvent is cellosolvo, 2-methyl cellosolve, 1,3-PD, 1,2-PD, ethylene glycol or glycerol; The volume ratio of described water-miscible organic solvent and water is arbitrary proportion.
3. synthetic method according to claim 1, described three halogenation iridium hydrates are iridous chloride hydrate, tribromide iridium hydrate.
4. synthetic method according to claim 1, reaction terminates direct filtration, and the product purity 99% obtained, reaches industrial application requirement.
5. synthetic method according to claim 1, the add-on of catalyzer X is L
2ir (μ-X)
2irL
21% ~ 10 times; The add-on of part C is L
2ir (μ-X)
2irL
22 ~ 20 times.
6. synthetic method according to claim 1, the temperature of reaction that adds of catalyzer X is-50 DEG C ~ 100 DEG C.
7. synthetic method according to claim 5, the add-on of catalyzer X is L
2ir (μ-X)
2irL
25% ~ 8 times; The add-on of part C is L
2ir (μ-X)
2irL
22 ~ 10 times.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210353282.4A CN102887922B (en) | 2012-09-21 | 2012-09-21 | A kind of synthetic method of iridium compounds |
| PCT/CN2013/082066 WO2014044110A1 (en) | 2012-09-21 | 2013-08-22 | Synthetic method of iridium compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210353282.4A CN102887922B (en) | 2012-09-21 | 2012-09-21 | A kind of synthetic method of iridium compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102887922A CN102887922A (en) | 2013-01-23 |
| CN102887922B true CN102887922B (en) | 2015-09-02 |
Family
ID=47531616
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210353282.4A Active CN102887922B (en) | 2012-09-21 | 2012-09-21 | A kind of synthetic method of iridium compounds |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102887922B (en) |
| WO (1) | WO2014044110A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102887922B (en) * | 2012-09-21 | 2015-09-02 | 赵洪玉 | A kind of synthetic method of iridium compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146099A (en) * | 2010-02-09 | 2011-08-10 | 北京阿格蕾雅科技发展有限公司 | Synthesis method of organic-metallic iridium compound |
| CN102603802A (en) * | 2011-12-22 | 2012-07-25 | 南京邮电大学 | Phosphorescent Iridium complex using thienyl benzothiazole derivative as ligand as well as preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3883570A (en) * | 1970-09-24 | 1975-05-13 | Du Pont | Bis(dialkylaminomethyl)-phenylenedipalladium (II) compounds |
| CN102887922B (en) * | 2012-09-21 | 2015-09-02 | 赵洪玉 | A kind of synthetic method of iridium compounds |
-
2012
- 2012-09-21 CN CN201210353282.4A patent/CN102887922B/en active Active
-
2013
- 2013-08-22 WO PCT/CN2013/082066 patent/WO2014044110A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102146099A (en) * | 2010-02-09 | 2011-08-10 | 北京阿格蕾雅科技发展有限公司 | Synthesis method of organic-metallic iridium compound |
| CN102603802A (en) * | 2011-12-22 | 2012-07-25 | 南京邮电大学 | Phosphorescent Iridium complex using thienyl benzothiazole derivative as ligand as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014044110A1 (en) | 2014-03-27 |
| CN102887922A (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101679856A (en) | Novel organometallic complexes that emit light in the red to green spectral range and their use in OLEDs | |
| CN103880867B (en) | A kind of double-core cuprous coordination compound green luminescent material and preparation method thereof | |
| CN104370974A (en) | Iridium complex taking nitrogen heterocyclic carbenes as second primary ligand and preparation method of said iridium complex | |
| CN107325130A (en) | The synthesis of Xin Xing perylene diimide class annular metal iridium complexes and its application for regulating and controlling phosphorescence dual emission using solution concentration | |
| CN105924469A (en) | Crystalline benzimidazolyl quinoline cuprous complex luminescent material | |
| CN102757466B (en) | Ir (III)-Eu (III) thermometal complex and application thereof | |
| CN104311588A (en) | Silafluorene-based aggregation-induced emission molecule as well as preparation method and application thereof | |
| CN110845741B (en) | One-dimensional silver cluster coordination polymer and preparation method and application thereof | |
| CN102887922B (en) | A kind of synthetic method of iridium compounds | |
| CN103497219A (en) | Red-light iridium complexes and application thereof in organic white or red electroluminescence device | |
| Liu et al. | Single-molecule white-light of tris-pyrazolonate-Dy3+ complexes | |
| CN101898997A (en) | Method for preparing novel zinc terpyridine blue fluorescent powder | |
| CN105694868A (en) | Benzimidazolyl-quinoline cuprous complex light-emitting material | |
| CN104788499A (en) | Spirobifluorene trifluoromethyl pyridine iridium complex as well as preparation method and application thereof | |
| CN103865523A (en) | Double-core cuprous iodide complex luminescent material | |
| CN103571454A (en) | Iridium containing organic electroluminescent material, preparation method thereof and organic electroluminescent device | |
| CN104004509A (en) | Organo-boron group-containing phosphorescent organic electroluminescent material and preparation method thereof | |
| CN104086598A (en) | Ionic iridium complex with bidentate ligand, and preparation method and application thereof | |
| CN104844629B (en) | A kind of monokaryon copper [I] complex material of blue or/and green emission | |
| WO2021036978A1 (en) | Tetradentate ligands, gold(iii) complexes, preparation method and use thereof | |
| CN108948094B (en) | C ^ N bidentate organic conjugated ligand inlaid with butterfly structure and cyclometalated iridium complex monomolecular white light material thereof | |
| KR101450587B1 (en) | new platinum complex, manufacturing method thereof and organic light emitting diode containing the same | |
| CN106946945B (en) | Orange light metal iridium complex phosphor material and preparation method thereof | |
| TWI422591B (en) | Synthesis of Organic Metal Iridium Compounds | |
| CN106085413B (en) | A kind of narrow emission hybrid inorganic-organic red light material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160202 Address after: 100086, No. 21, building 1, No. 12, Zhongguancun South Avenue, Beijing, Haidian District, 2506 Patentee after: BEIJING TUOCAI PHOTOELECTRIC TECHNOLOGY Co.,Ltd. Address before: 100088, No. 28, Xin Wai Avenue, Beijing, Xicheng District Patentee before: Zhao Hongyu |