CN108586536A - 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs and synthetic method - Google Patents
2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs and synthetic method Download PDFInfo
- Publication number
- CN108586536A CN108586536A CN201810698718.0A CN201810698718A CN108586536A CN 108586536 A CN108586536 A CN 108586536A CN 201810698718 A CN201810698718 A CN 201810698718A CN 108586536 A CN108586536 A CN 108586536A
- Authority
- CN
- China
- Prior art keywords
- phenyl
- phosphine
- dimethylaniline
- dimethylaminophenyls
- synthetic method
- 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.)
- Granted
Links
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title claims abstract description 32
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 32
- 229910021595 Copper(I) iodide Inorganic materials 0.000 title claims abstract description 26
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 238000010189 synthetic method Methods 0.000 title claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003446 ligand Substances 0.000 claims abstract description 22
- -1 dimethylaminophenyl Chemical group 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims abstract description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 6
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 3
- ONMSBNJJCUCYED-UHFFFAOYSA-N 2-bromo-n,n-dimethylaniline Chemical class CN(C)C1=CC=CC=C1Br ONMSBNJJCUCYED-UHFFFAOYSA-N 0.000 claims description 8
- 150000004694 iodide salts Chemical class 0.000 claims description 6
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- GUAWMXYQZKVRCW-UHFFFAOYSA-N n,2-dimethylaniline Chemical compound CNC1=CC=CC=C1C GUAWMXYQZKVRCW-UHFFFAOYSA-N 0.000 claims 5
- CDYASPZPWAFLMW-UHFFFAOYSA-N N,1-dimethylcyclohexa-2,4-dien-1-amine Chemical compound CNC1(CC=CC=C1)C CDYASPZPWAFLMW-UHFFFAOYSA-N 0.000 claims 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract 2
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 43
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 13
- 239000010949 copper Substances 0.000 description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000011574 phosphorus Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- CZZBXGOYISFHRY-UHFFFAOYSA-N copper;hydroiodide Chemical compound [Cu].I CZZBXGOYISFHRY-UHFFFAOYSA-N 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910017489 Cu I Inorganic materials 0.000 description 3
- 229910017888 Cu—P Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000002447 crystallographic data Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- TXWRERCHRDBNLG-UHFFFAOYSA-N cubane Chemical compound C12C3C4C1C1C4C3C12 TXWRERCHRDBNLG-UHFFFAOYSA-N 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6596—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms
-
- 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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
-
- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
Abstract
The present invention relates to 2 [(2 dimethylaminophenyl) (phenyl) phosphine] N, N dimethylaniline cuprous iodide complexs and its synthetic method and application, 2 bromanilines and iodomethane substitution reaction first and generate N by the present invention occur, 2 bromaniline of N dimethyl, then by the N, 2 bromaniline of N dimethyl, which is reacted with n-BuLi in tetrahydrofuran solution, generates aryl lithium；The aryl lithium is continued to generate ligand 2 [(2 dimethylaminophenyl) (phenyl) phosphine] N with dichloro- phenyl phosphine reaction, N dimethylanilines (ppda), finally, the ppda is reacted with cuprous iodide in dichloromethane solution, the target product is obtained.High using the method for the present invention synthesis target product yield, up to 72%, and synthetic method of the present invention is simple, easy to operate.In addition, the target product of the present invention has double emission characteristics, luminescent material assembling OLED is can be used as, is had a good application prospect.
Description
Technical field
The invention belongs to luminescent material technical fields, it is more particularly related to a kind of 2- [(2- Dimethylaminobenzenes
Base) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs and its synthetic method.
Background technology
Compared to monokaryon and the cuprous complex of double-core, the cuprous cluster compound of multinuclear often shines with thermochromism
The characteristic of (Luminescence thermochromism) and double transmittings (Dual emission).In cuprous complex, hair
The mode of light has diversity, is divided into local excitation (Local excitation, LE), electric charge transfer (Charge
Transfer, CT) transition and cluster center (Cluster centered, CC) shine.Xu and its partner report one kind and contain
Four core cuprous iodide cluster compounds of oxa- fluorenes biphosphine ligand, copper iodine cluster have the structure of similar cubane, and its electroluminescent
The TADF of blue and the overall characteristic that orange-red cluster compound is luminous are contained, is in white light emission.Perruchas etc. reports one
Six core cuprous iodide cluster compounds of the kind containing the double phosphines of propylidene, this cluster compound is with the reduction of temperature, and emission spectrum is 413
There is enhancing with the intensity of two emission peaks at 673nm, shows thermochromism (Thermochromic
Luminescence) luminous characteristic.
Recently, Zhang etc. reports a series of monokaryon cuprous halide complexs containing three tooth Phosphine ligands, has stronger
Green emission, quantum yield are up to 83%, by its construction OLED maximum EQE up to 16.3%.This monokaryon cuprous halide
Complex has typical TADF phenomenons, and phosphorescence intensity accounts for total luminous intensity nearly 100% when 77K, and TADF intensity accounts for when room temperature
Total luminous intensity about 60%.A series of double-core halogenation that Yersin etc. reports triphenylphosphine derivates containing dimethylamino is sub-
Copper complex, there is a stronger bluish-green light emitting, and maximum photoluminescence quantum efficiencies are up to 65%.
Application of neutral copper (I) complex and its cluster compound of tridentate ligand in OLED has great potential, and related
Report it is seldom.Based on this, the application is made.
Invention content
In view of the problems of the existing technology, the purpose of the present invention is to provide 2- [(2- dimethylaminophenyls) (phenyl)
Phosphine]-N, N- dimethylaniline cuprous iodide complexs and its synthetic method.The complex of the present invention closes for six core cuprous iodide clusters
Object reacts generation with cuprous iodide by phenyl dinitrogen list phosphine tridentate ligand.
In order to realize that above-mentioned first purpose of the present invention, the present invention adopt the following technical scheme that：
2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs, empirical formula are：
C44H50Cu6I6N4P2, molecular weight 1839.46, the complex is monoclinic system, P2 (1)/n space groups, cell parameterThe complex molecule structural formula
As shown in following formula one：
Another object of the present invention is to provide 2- described above [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- bis-
The synthetic method of toluidines cuprous iodide complex, described method includes following steps：
First, substitution reaction is occurred into for 2- bromanilines and iodomethane and generates N, N- dimethyl -2- bromanilines then will be described
N, N- dimethyl -2- bromanilines, which are reacted with n-BuLi in tetrahydrofuran solution, generates aryl lithium；By the aryl lithium after
Continuous and dichloro- phenyl phosphine reaction generation ligand 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylanilines (ppda),
Finally, the ppda is reacted with cuprous iodide in dichloromethane solution, obtains the 2- [(2- dimethylaminophenyls)
(phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs.
2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N described above, the synthesis of N- dimethylaniline cuprous iodide complexs
Route is as shown in formula two：
Further, the molar ratio of the 2- bromanilines and iodomethane described in above-mentioned technical proposal is 1：5.
Further, the molar ratio of the N described in above-mentioned technical proposal, N- dimethyl -2- bromanilines and n-BuLi is
1：1.
Further, mole of the N described in above-mentioned technical proposal, N- dimethyl -2- bromanilines and dichloro- phenyl phosphorus
Than being 2：1.
Further, the molar ratio of the ligand ppda and cuprous iodide described in above-mentioned technical proposal are 1：1.
Further, the proportioning of the ligand ppda and dichloromethane described in above-mentioned technical proposal are 0.105g：30mL.
A further purpose of the present invention is to provide target product 2- described above [(2- dimethylaminophenyls) (phenyl)
Phosphine]-N, the application of N- dimethylaniline cuprous iodide complexs, can be used as luminescent material assembling OLED.
A kind of assembling OLED luminescent materials, the luminescent material are present invention 2- [(2- Dimethylaminobenzenes described above
Base) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs.
Compared with prior art, the present invention has the advantages that：
(1) yield using present invention synthesis target product is high, and up to 72%, and synthetic method of the present invention is simple, easy to operate,
Expensive instrument and equipment is not needed, industrialization is conducive to；
(2) target product 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N produced by the present invention, N- dimethylaniline iodate
Cuprous complex is a kind of novel copper iodine cluster compound containing dinitrogen list phosphorus tridentate ligand, has double emission characteristics, maximum hair
Ejected wave a length of 474nm emits white light under solid-state, and the S of target product1And T1Between energy gap Δ E (S1-T1) smaller, show the production
Object at room temperature luminous belongs to hot activation delayed fluorescence, and for light sources in MLCT and XLCT, solid state quantum yield is 14.8%,
Therefore, target product produced by the present invention can be used as luminescent material assembling OLED, have a good application prospect.
Description of the drawings
Fig. 1 is 2- made from the embodiment of the present invention 1 [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylanilines
(ppda) in CDCl3In nuclear magnetic resonance spectroscopy；
Fig. 2 is target product made from the embodiment of the present invention 1 in CDCl3In nuclear magnetic resonance spectroscopy；
Fig. 3 is 2- made from the embodiment of the present invention 1 [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylanilines
(ppda) in CDCl3In nuclear magnetic resonance phosphorus spectrum；
Fig. 4 is target product made from the embodiment of the present invention 1 in CDCl3In nuclear magnetic resonance phosphorus spectrum；
Fig. 5 is the mass spectrogram of target product made from the embodiment of the present invention 1；
Fig. 6 is the crystal structure figure of target product made from the embodiment of the present invention 1；
Fig. 7 is ligand ppda and the target product uv-visible absorption spectroscopy comparison in acetonitrile respectively at 298K
Figure；
Fig. 8 is fluorescence spectrum of the target product at 298K made from the embodiment of the present invention 1.
Specific implementation mode
It elaborates below to the case study on implementation of the present invention.The implementation case under the premise of technical solution of the present invention into
Row is implemented, and gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following realities
Apply case.
The information for including according to the application, to those skilled in the art can be easily to the essence of the present invention
Really description carries out various changes, without departing from spirit and scope of the appended claims.It should be understood that the scope of the present invention is not
Process, property or component defined by being confined to, because these embodiments and other descriptions are just for the sake of schematic
Illustrate certain aspects of the present disclosure.In fact, this field or those skilled in the relevant art obviously can be to embodiment party of the present invention
The various changes that formula is made all cover within the scope of the appended claims.
For a better understanding of the present invention rather than limit the scope of the invention, expression dosage used in this application,
All numbers of percentage and other numerical value, are understood to " about " be modified with word in all cases.Therefore,
Unless stated otherwise, otherwise digital parameters listed in specification and appended book are all approximations, may
It can be changed according to the difference for the desirable properties for attempting to obtain.Each digital parameters at least should be considered as according to being reported
Effective digital and by it is conventional round up method by obtain.
Embodiment 1
2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N of the present embodiment, the conjunction of N- dimethylaniline cuprous iodide complexs
At method, specifically comprise the following steps：
(1) synthesis of N, N- dimethyl -2- bromanilines
The synthesis of the substance has references to previously reported document (Bonnaventure I, Charette AB.Probing
the importance of the hemilabile site of bis(phosphine)monoxide ligands in
the copper-catalyzed addition of diethylzinc to N-phosphinoylimines:Discovery
of new effective chiral ligands[J].The Journal of Organic Chemistry,2008,73
(16):6330-6340.).Specific synthesis step is as follows：
In the round-bottomed flask of 250mL, 4.0g (23.3mmol) 2- bromanilines, 16.1g (116.5mmol) anhydrous carbon is added
Sour potassium, 7.3mL (116.5mmol) iodomethane (CH3I) and 50mL acetonitriles (MeCN), it is heated to 70 DEG C.18h is stirred at 70 DEG C
Afterwards, cooling reaction mixture is extracted to room temperature using 100mL deionized waters and 100mL ether.After organic phase is separated, make
Water phase is washed with 3 × 50mL ether.Organic phase after being merged using the saturated common salt water washing of 5 × 50mL is then used anhydrous
Magnesium sulfate dries organic phase.Next, vacuum distillation removes volatile components in organic phase, crude product is obtained.Crude product is through silicagel column
Chromatography obtains the flaxen oily liquids of 2.7g, and eluant, eluent is ether/hexane (5/95v/v), yield 69%.Relevant characterization
Data are consistent with the above-mentioned document reported.
(2) 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, the synthesis of N- dimethylanilines (ppda)
Under -120 DEG C, nitrogen atmosphere, to 20mL tetrahydrofurans/ether of 1g (5mmol) N, N- dimethyl -2- bromanilines
In (1/1v/v) solution, the hexane solution of the n-BuLi of 2.5M 2.01mL (5mmol) is added dropwise dropwise, and in same temperature
Lower heat preservation 1h.Next, at the same temperature, 0.33mL (2.5mmol) dichlorobenzene is added dropwise dropwise into reaction mixture
Base phosphorus.Drop finishes, and reaction mixture is in faint yellow, removes ice bath, stirring at normal temperature is overnight.Finally, by dilute salt of a concentration of 1M of 10mL
Acid is added in reaction mixture, dichloromethane extraction, saturated ammonium chloride solution washing.After organic phase merges, through anhydrous sodium sulfate
It is dry, and removing volatile components are evaporated under reduced pressure, residue obtains 0.87g white powders through silica gel column chromatography separating-purifying, washes
De- agent is dichloromethane/hexane (1/4v/v), yield 50%.
(3) target product 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs
Synthesis
Take ligand ppda (0.105g, 0.30mmol) and cuprous iodide (0.057g, 0.30mmol) in dry flask it
In, 30mL dichloromethane, and stirring at normal temperature 3h under nitrogen atmosphere is added, finally obtained the suspension of white.Filtering retains
Filtrate is used in combination 5 × 10mL dichloromethane to wash filter residue.Filter residue is dissolved in dichloromethane/acetonitrile, is placed at room temperature, through solvent
Slowly volatilization, can be obtained the crystal of target product, yield 0.397g, yield 72%.
Nuclear-magnetism is respectively adopted in ppda and target product that 1 step of above-described embodiment (2), step (3) are prepared
(600MHz,1H NMR) it is characterized, test result is respectively referring to Fig. 1, Fig. 2.
As can be seen from Figure 1：
Test result is as follows by ppda：
1H NMR(600MHz,CDCl3):δ:7.31,7.26 (m, 5H), 7.19,7.17 (m, 4H), 6.96 (t, J=12Hz,
2H),6.80,6.79(m,2H),2.63(s,12H).
As can be seen from Figure 2：
Target product 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, the test of N- dimethylaniline cuprous iodide complexs
As a result as follows：
1H NMR(600MHz,CDCl3)δ:7.84,7.77(m,2H),7.68,7.55(m,6H),7.47,7.39(m,
12H),7.18(m,6H),2.67(s,24H).
In addition, ppda and target product that 1 step of above-described embodiment (2), step (3) are prepared are in CDCl3In
Nuclear magnetic resonance phosphorus is composed, and the phosphorus of ligand ppda is composed as shown in figure 3, test result is as follows：
31P NMR(240M,CDCl3)δ:-17.45(s).
The phosphorus of target product is composed as shown in figure 4, test result is as follows：
31P NMR(240M,CDCl3)δ:-31.73.
By above-mentioned phosphorus spectrum as can be seen that ligand ppda and target product chemical shift be respectively -17.45ppm with -
31.73ppm.Complex nuclear magnetic resonance phosphorus spectrum in signal peak all be it is unimodal, this illustrate complex have on molecular structure compared with
Good symmetry.
Fig. 5 is the mass spectrogram of target product of the present invention.Mass spectrum uses Matrix Assisted Laser Desorption time-of-flight mass spectrometry
(MALDI-TOF MS) is tested, and specific test result is as follows：
Anal.Calcd for C44H50Cu6I6N4P2:C,28.73；H,2.74；N,3.05.Found:C,28.71；H,
2.75；N,3.05.MS(MALDI-TOF):m/z calcd for[C22H25Cu2IN2P]+,601.9426,found:
601.3938.
By the collection of illustrative plates it is found that target product has stronger peak in mass-to-charge ratio for 601.3938, mesh can be attributed to
Mark product has been broken the [Cu obtained after 3 Cu-I keys2I(ppda)]+Fragment ion.
Fig. 6 is the crystal structure figure of target product made from the above embodiment of the present invention 1.In addition, table 1 is target product
Crystallographic data and part bond distanceWith bond angle (°) data.
The crystallographic data table of 1 target product of table
The part bond distance of 2 target product of tableWith bond angle (°) tables of data
As seen from Figure 6, in the structure of target product, there are two ppda ligands by the Cu of a similar chair form6I6Core
Package.The crystallographic data and part bond distance and bond angle data of target product is set forth in Tables 1 and 2.Target product has
There are one Cu6I6Nutty structure, all copper atoms all be four-coordination configuration, wherein four be CuPNI2Structure and another two
For CuI4Structure.In target product, the bond distance of the bond distance of Cu-I keys and the copper iodine cluster compound reported is without significant difference.And
Cu-N keys bond distance (With) compared to binuclear complex [Cu (μ-I) (PNMe2)]2Cu-P keys key
Long (With) outline is shorter, which reflects the coordinate bonds in target product between copper atom and nitrogen-atoms
It is stronger.And in target product Cu-P keys bond distance (With) about than Cu-P keys in common cuprous complexBond distance want longer, the steric hindrance that this can be attributed in target product around phosphorus atoms is larger.Due to 2
The sum of the van der Waals radius of cuprous atom isCu ... Cu distances are in target productIllustrate to match at this
Closing has certain Cu ... Cu interaction forces in object.There is also intermolecular hydrogen bondings in target product, between H and I
The shortest distance isIn target product, there are intermolecular C-H ... π interactions, H between the phenyl ring being connected with N, P
The shortest distance between C isIn addition, between the phenyl ring and methyl that are connected with nitrogen-atoms, there is also intermolecular C-H ...
π interacts, and the shortest distance between H and H, between H and C is respectivelyWithAs shown in figure 5, these C-
H ... π interaction forces make target product have along a, the 1-D banded structures of b and c-axis.In target product, Cu-Cu-I are flat
The dihedral angle of face and phenyl ring plane minimum is 7.16 °.
Fig. 7 is illustrated at room temperature, the uv-visible absorption spectroscopy of ligand ppda and target product in acetonitrile, dense
Degree is 5.5 × 10-6M.As seen from Figure 7, ligand ppda has at a length of 211nm of maximum absorption wave compared with strong absworption peak, maximum
Molar extinction coefficient ε is 2.80 × 104M-1cm-1, this is the ultraviolet peak of the characteristic absorption of aromatic phosphines and aromatic amine compound.This is inhaled
The mixing transition of n → π * and π → π * in ligand ppda can be attributed to by receiving bands of a spectrum.Target product is a length of in maximum absorption wave
There are stronger absorption band (ε=1.86 × 10 at 245nm4M-1cm-1), and wave-length coverage be 320-360nm place there are one compared with
Weak absorption tail band.This weaker tail band can be attributed to caused by MLCT and XLCT transition.
Fig. 8 is excitation wavelength lambdaexcFor 367nm when, emission spectrum of the target product at 298K.At 298K, target production
Object shows a kind of shining for white, and cie color coordinate is (0.2297,0.2737), maximum emission wavelength λmaxFor 474nm.
Luminescent lifetime of the target product at 298K is shorter (2.7 μ s), it is meant that target product has TADF luminescence phenomenons.
In addition, by Fig. 8 can also be seen that target product in 420nm there are one acromion, 715nm at there are one it is weak and
Wide emission peak, the former can be attributed to local excitation (LE) and shine, and the latter is copper iodine cluster center (Cluster Center) hair
Light.
Claims (9)
1.2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs, it is characterised in that：It is described
The empirical formula of complex is：C44H50Cu6I6N4P2, molecular weight 1839.46, the complex is monoclinic system, and P2 (1)/n is empty
Between group, cell parameterThe complex
Molecular structural formula is as shown in following formula one：
2. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N described in claim 1, N- dimethylaniline cuprous iodide complexs
Synthetic method, it is characterised in that：Described method includes following steps：
First, substitution reaction is occurred into for 2- bromanilines and iodomethane and generates N, N- dimethyl -2- bromanilines, then by the N, N-
Dimethyl -2- bromanilines, which are reacted with n-BuLi in tetrahydrofuran solution, generates aryl lithium；By the aryl lithium continue with
Dichloro- phenyl phosphine reaction generation ligand 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylanilines (ppda), finally,
The ppda is reacted with cuprous iodide in dichloromethane solution, target product is obtained.
3. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N according to claim 2, N- dimethylaniline cuprous iodides are matched
Close the synthetic method of object, it is characterised in that：The molar ratio of the 2- bromanilines and iodomethane is 1：5.
4. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N according to claim 2, N- dimethylaniline cuprous iodides are matched
Close the synthetic method of object, it is characterised in that：The molar ratio of the N, N- dimethyl -2- bromanilines and n-BuLi is 1：1.
5. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N according to claim 2, N- dimethylaniline cuprous iodides are matched
Close the synthetic method of object, it is characterised in that：The molar ratio of the N, N- dimethyl -2- bromanilines and dichloro- phenyl phosphorus is 2：
1。
6. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N according to claim 2, N- dimethylaniline cuprous iodides are matched
Close the synthetic method of object, it is characterised in that：The molar ratio of the ligand ppda and cuprous iodide is 1：1.
7. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N according to claim 2, N- dimethylaniline cuprous iodides are matched
Close the synthetic method of object, it is characterised in that：The proportioning of the ligand ppda and dichloromethane is 0.105g：30mL.
8. 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N described in claim 1, N- dimethylaniline cuprous iodide complexs
Application, it is characterised in that：The complex can be used as luminescent material assembling OLED.
9. a kind of assembling OLED luminescent materials, it is characterised in that：The luminescent material is 2- described in claim 1 [(2- bis-
Methylaminophenyl) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810698718.0A CN108586536B (en) | 2018-06-29 | 2018-06-29 | 2- [ (2-dimethylamino phenyl) (phenyl) phosphine ] -N, N-dimethylaniline cuprous iodide complex and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810698718.0A CN108586536B (en) | 2018-06-29 | 2018-06-29 | 2- [ (2-dimethylamino phenyl) (phenyl) phosphine ] -N, N-dimethylaniline cuprous iodide complex and synthetic method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108586536A true CN108586536A (en) | 2018-09-28 |
| CN108586536B CN108586536B (en) | 2020-04-28 |
Family
ID=63634641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810698718.0A Active CN108586536B (en) | 2018-06-29 | 2018-06-29 | 2- [ (2-dimethylamino phenyl) (phenyl) phosphine ] -N, N-dimethylaniline cuprous iodide complex and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108586536B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824722A (en) * | 2019-02-26 | 2019-05-31 | 湖北大学 | Dinitrogen list phosphine compound and its preparation method and application and cuprous halide complex and its preparation method and application |
| CN111233924A (en) * | 2020-01-15 | 2020-06-05 | 湖北大学 | Carbazole derivative and preparation method thereof, cuprous halide nanocluster compound and preparation method, application and device thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880867A (en) * | 2014-03-03 | 2014-06-25 | 中国计量学院 | Di-nuclear cuprous complex green luminescent material and preparation method thereof |
| CN104830321A (en) * | 2015-05-21 | 2015-08-12 | 中国计量学院 | Three-coordination dual-core copper iodide complex light-emitting material |
| CN104893715A (en) * | 2015-05-21 | 2015-09-09 | 中国计量学院 | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core |
| CN104910897A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cu3I2 cationic cuprous cluster compound green phosphor material |
| CN105153230A (en) * | 2015-07-02 | 2015-12-16 | 浙江理工大学 | Azafluorene and phosphine blended tricoordinated copper iodide complex luminescent material |
| CN105859752A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Benzoxazole pyridine-based copper iodide complex orange luminous material |
-
2018
- 2018-06-29 CN CN201810698718.0A patent/CN108586536B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103880867A (en) * | 2014-03-03 | 2014-06-25 | 中国计量学院 | Di-nuclear cuprous complex green luminescent material and preparation method thereof |
| CN104830321A (en) * | 2015-05-21 | 2015-08-12 | 中国计量学院 | Three-coordination dual-core copper iodide complex light-emitting material |
| CN104893715A (en) * | 2015-05-21 | 2015-09-09 | 中国计量学院 | Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core |
| CN104910897A (en) * | 2015-06-17 | 2015-09-16 | 中国计量学院 | Cu3I2 cationic cuprous cluster compound green phosphor material |
| CN105153230A (en) * | 2015-07-02 | 2015-12-16 | 浙江理工大学 | Azafluorene and phosphine blended tricoordinated copper iodide complex luminescent material |
| CN105859752A (en) * | 2016-05-05 | 2016-08-17 | 中国计量大学 | Benzoxazole pyridine-based copper iodide complex orange luminous material |
Non-Patent Citations (1)
| Title |
|---|
| KAZUSHI MASHIMA ET AL.: "Chemoselective asymmetric hydrogenation of alpha, beta-unsaturated carbonyl compounds to allylic alcohols catalysed by [Ir(binap)(cod)]BF4,-aminophosphine", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109824722A (en) * | 2019-02-26 | 2019-05-31 | 湖北大学 | Dinitrogen list phosphine compound and its preparation method and application and cuprous halide complex and its preparation method and application |
| CN109824722B (en) * | 2019-02-26 | 2021-06-11 | 湖北大学 | Bisphosphoryl monophosphine compound, preparation method and application thereof, cuprous halide complex, preparation method and application thereof |
| CN111233924A (en) * | 2020-01-15 | 2020-06-05 | 湖北大学 | Carbazole derivative and preparation method thereof, cuprous halide nanocluster compound and preparation method, application and device thereof |
| CN111233924B (en) * | 2020-01-15 | 2022-02-18 | 湖北大学 | Carbazole derivative and preparation method thereof, cuprous halide nanocluster compound and preparation method, application and device thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108586536B (en) | 2020-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Costa et al. | Copper (I) complexes for sustainable light-emitting electrochemical cells | |
| Shan et al. | Intramolecular π-stacking in cationic iridium (iii) complexes with a triazole–pyridine type ancillary ligand: synthesis, photophysics, electrochemistry properties and piezochromic behavior | |
| Deng et al. | Diphenylphosphorylpyridine-functionalized iridium complexes for high-efficiency monochromic and white organic light-emitting diodes | |
| Adamovich et al. | Preparation of tris-heteroleptic iridium (III) complexes containing a cyclometalated aryl-N-heterocyclic carbene ligand | |
| WO2012162488A1 (en) | Synthesis of platinum and palladium complexes as narrow-band phosphorescent emitters for full color displays | |
| Mondal et al. | Nickel (II), copper (I) and zinc (II) complexes supported by a (4-diphenylphosphino) phenanthridine ligand | |
| Zhang et al. | Photo-and electro-luminescence of four cuprous complexes with sterically demanding and hole transmitting diimine ligands | |
| Yan et al. | Regioselective Syntheses of Imidazo [4, 5-b] pyrazin-2-ylidene-Based Chelates and Blue Emissive Iridium (III) Phosphors for Solution-Processed OLEDs | |
| Lee et al. | Deep-blue phosphorescent iridium (III) dyes based on fluorine-functionalized bis (2, 3′-bipyridyl) ligand for efficient organic light-emitting diodes | |
| Chien et al. | Stepwise and one-pot syntheses of Ir (III) complexes with imidazolium-based carbene ligands | |
| Huang et al. | Structural characterization, electronic and luminescent properties of copper (I) complexes with different temperatures and their application to light-emitting diodes | |
| CN108586536A (en) | 2- [(2- dimethylaminophenyls) (phenyl) phosphine]-N, N- dimethylaniline cuprous iodide complexs and synthetic method | |
| CN109824722B (en) | Bisphosphoryl monophosphine compound, preparation method and application thereof, cuprous halide complex, preparation method and application thereof | |
| Wu et al. | Synthesis, structures, DFT studies and luminescent properties of copper (I)-diimine complexes and application in yellow-green light-emitting diode | |
| CN108752382B (en) | Terphenyl diphosphine three-coordination cuprous halide complex, and synthesis method and application thereof | |
| Luo et al. | Synthesis, optoelectronic properties of a dinuclear platinum (II) complex containing a binary cyclometalated ligand in the single-emissive-layer PLEDs | |
| Cañada et al. | Blue-phosphorescent bis-cyclometalated iridium complexes with aryl isocyanide ancillary ligands | |
| Wen et al. | Boosting the efficiency of deep-red Ir (III) complexes by modulating nitrogen atoms for high-performance OLEDs | |
| KR101335548B1 (en) | platinum complex for phosphorescent materials and organic electroluminescent device containing the same | |
| Zhao et al. | Fluoro-benzenesulfonyl-functionalized 2-phenylthiazole-type iridium (iii) complexes for efficient solution-processed organic light-emitting diodes | |
| Yang et al. | Bathochromic effect of trifluoromethyl-substituted 2-naphthalen-1-yl-pyridine ligands in color tuning of iridium complexes | |
| Chen et al. | Synthesis, crystal structures and photophysical properties of novel copper (I) complexes with 4-diphenylphosphino-1, 5-naphthyridine ligands | |
| Tao et al. | Highly efficient and concentration-insensitive OLEDs based on alkyl sterically modified red homoleptic phenylphthalazine iridium complexes | |
| CN109678907B (en) | Metal platinum (II) complex containing bridged phenyl-pyrazole structural unit | |
| CN109678906B (en) | Metal platinum (II) complex containing double-bridged phenyl-pyrazole structural unit and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |