CN110016051A - Diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex and its synthetic method, application and device - Google Patents
Diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex and its synthetic method, application and device Download PDFInfo
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- CN110016051A CN110016051A CN201910324946.6A CN201910324946A CN110016051A CN 110016051 A CN110016051 A CN 110016051A CN 201910324946 A CN201910324946 A CN 201910324946A CN 110016051 A CN110016051 A CN 110016051A
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- complex
- quinolyl
- diphenyl
- phosphine
- cuprous halide
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- KEJUJPUDSJXTMZ-UHFFFAOYSA-N diphenyl(quinolin-8-yl)phosphane Chemical compound C1=CC=CC=C1P(C=1C2=NC=CC=C2C=CC=1)C1=CC=CC=C1 KEJUJPUDSJXTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 150000004820 halides Chemical class 0.000 title claims abstract description 19
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- 239000000463 material Substances 0.000 claims description 13
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 230000003111 delayed effect Effects 0.000 claims description 5
- 238000007725 thermal activation Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 2
- NGWRWXZTTCRVJE-UHFFFAOYSA-N 1,2,3,6-tetrahydrophosphinine Chemical compound C1CC=CCP1 NGWRWXZTTCRVJE-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 16
- 239000010949 copper Substances 0.000 abstract description 14
- 239000007787 solid Substances 0.000 abstract description 11
- 150000004699 copper complex Chemical class 0.000 abstract description 2
- -1 diphenyl -8- quinolyl phosphine triphenylphosphine Chemical compound 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 19
- 239000013078 crystal Substances 0.000 description 15
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 229910052736 halogen Inorganic materials 0.000 description 9
- 150000002367 halogens Chemical class 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 7
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 230000005281 excited state Effects 0.000 description 3
- 230000003760 hair shine Effects 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910017489 Cu I Inorganic materials 0.000 description 1
- 229910017888 Cu—P Inorganic materials 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- INODPMZPXPDHAV-UHFFFAOYSA-N N1=CC=CC2=CC=CC(=C12)PC1=CC=CC=C1 Chemical compound N1=CC=CC2=CC=CC(=C12)PC1=CC=CC=C1 INODPMZPXPDHAV-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004773 frontier orbital Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- JWTSNWDILVPNHA-UHFFFAOYSA-N phosphane;quinoline Chemical compound P.N1=CC=CC2=CC=CC=C21 JWTSNWDILVPNHA-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/576—Six-membered rings
- C07F9/60—Quinoline or hydrogenated quinoline ring 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
- 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
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to copper complex technical fields, and in particular to diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex and its synthetic method, application and device.Complex provided by the present invention has containing the mixed structure of monokaryon Cu (I) with two kinds of ligands of diphenyl -8- quinolyl phosphine triphenylphosphine, enhances the rigid structure of molecule entirety, improves the solid state quantum efficiency of complex.
Description
Technical field
The invention belongs to copper complex technical fields, and in particular to diphenyl -8- quinolyl phosphine and triphenylphosphine mixture halogen
Change cuprous complex and its synthetic method, application and device.
Background technique
In recent years, OLED (Organic Light Emitting Diode) due to can self-luminous, visibility is high, reacts fast, light-weight, thickness
It is thin, building it is simple the advantages that, be considered as one of the product of 21 century most future.With Pt2+、Ir3+、Os2+And Ru2+Equal noble metals
The metal complex OLED device developed shows outstanding luminescent properties.But since this kind of noble metal is more high in price
It is expensive, pollution is be easy to cause to environment, so copper (I) complex of exploitation high performance electrophosphorescenoleds causes various countries scientific worker's
Pay attention to.But for Cu (I) complex of current monophosphorus ligand since structural rigidity is poor, energy is easy to happen non-radiative decay, makes
It is low at the luminous efficiency of complex.
Summary of the invention
To solve the deficiencies in the prior art, the present invention provides diphenyl -8- quinolyl phosphines and the halogenation of triphenylphosphine mixture
Cuprous complex and its synthetic method, application and device.Diphenyl -8- quinolyl phosphine provided by the present invention and triphenylphosphine are mixed
Mulecular luminescence efficiency is improved with rigid structure possessed by cuprous halide complex.
Technical solution provided by the present invention is as follows:
Diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex, general structure are as follows:
Wherein, X is Br or I.
In above-mentioned technical proposal, the N^P in diphenyl -8- quinolyl Phosphine ligands molecule can occur coordination with Cu and be formed
Enclosed construction with rigidity, can make the steric configuration of molecule more stable in this way.Meanwhile containing N, the miscellaneous distribution type of P atom
Complex is due to the MLCT excitation state with higher-energy, it is possible to reduce the non-radiative decay of energy improves molecule hair to reach
The purpose of light efficiency.But according to the report of document, the complex for the double-core four-coordination that diphenyl -8- quinolyl phosphine and CuI are formed
Good luminescent properties are not shown, and fluorescence quantum yield only has 1.6%.This is because this dual-core architecture by
After excitation, steric configuration is easy to be changed from original tetrahedral structure to planar shape structure, to make the energy of excitation state
Amount is dissipated in non-radiative mode.Therefore, the present invention joined on the basis of original complex by the modification of structure
Another ligand triphenylphosphine makes original dimeric structure become the mixed structure of monokaryon Cu (I) of the ligand containing there are two types of, in this way
The rigid structure of molecule entirety can be enhanced to a certain extent.Also, complex 1 and complex 2 all have good heat steady
It is qualitative.
Inventors have found that two kinds of complex maximum emission peaks are respectively 606nm and 620nm at normal temperature, the service life is respectively
7.58 μ s and 8.23 μ s, an order of magnitude shorter than the low temperature 77K service life.The singlet excited state S calculated according to DFT1It is excited with three lines
State T1Energy level difference distinguish 0.0232eV and 0.0119eV, be significantly smaller than 0.37eV, illustrate that shining for complex 1 and 2 is that heat is living
Change delayed fluorescence, shines and be mainly derived from MLCT and XLCT.The solid state quantum efficiency of complex 1 and 2 is respectively at room temperature
6.24% and 2.85%.Thermogravimetric analysis shows the thermal stability that 2 kinds of complexs have had.Based on material property, complex 1 and 2
Orange light luminescent material be can be used as applied to OLED.
Inventor has surprisingly been found that two kinds of complexs send out orange light at normal temperature.
The present invention also provides the synthesis sides of diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex
Method, comprising the following steps:
Wherein, X is Br or I.
Above-mentioned technical proposal, various substrates are easy to get, by a step can be prepared diphenyl -8- quinolyl phosphine with
Triphenylphosphine mixture cuprous halide complex, yield is high, is convenient for industrialized production.
The present invention also provides the applications of diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex, make
For fluorescent material.
Two kinds of complex maximum emission peaks are respectively 606nm and 620nm at normal temperature, and the service life is respectively 7.58 μ s and 8.23
μ s, the solid state quantum efficiency of complex 1 and 2 is respectively 6.24% and 2.85% at room temperature.
Further, as thermal activation delayed fluorescence material.
It is calculated according to DFT, at normal temperature the singlet excited state S of two kinds of complexs1With Triplet Excited State T1Energy level difference difference
0.0232eV and 0.0119eV, is significantly smaller than 0.37eV, illustrates shining as thermal activation delayed fluorescence, luminous master for complex 1 and 2
To derive from MLCT and XLCT.
Further, as orange light fluorescent material.
Based on room temperature luminous spectrum data, the CIE coordinate of complex 1 is (0.5616,0.436), and the CIE of complex 2 is sat
It is designated as (0.5795,0.4185), is orange light.The present invention provides the cuprous halide complex of hair orange light for the first time.
The present invention also provides the applications of diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex, make
For Organic Light Emitting Diode material.
The solid state quantum efficiency of complex 1 and 2 provided by the present invention at room temperature is respectively 6.24% and 2.85%, Gu
State quantum efficiency is high, can be applied to Organic Light Emitting Diode field.
The present invention also provides a kind of OLED device, include at least organic luminous layer, and the material of the organic luminous layer selects
The mixing of any one or two kinds in complex provided by the present invention.
Based on the characteristic of complex provided by the present invention, above-mentioned OLED device have high quantum efficiency, thermal stability,
Orange light can be sent out, there is good application value.
Detailed description of the invention
Fig. 1 is complex 1 provided by the present invention1H NMR spectra.
Fig. 2 is complex 2 provided by the present invention1H NMR spectra.
Fig. 3 is complex 1 provided by the present invention31P NMR spectra.
Fig. 4 is complex 2 provided by the present invention31P NMR spectra.
Fig. 5 is the mass spectrum of complex 1 provided by the present invention.
Fig. 6 is the mass spectrum of complex 2 provided by the present invention.
Fig. 7 is the crystal structure of complex 1 provided by the present invention.
Fig. 8 is the crystal structure of complex 2 provided by the present invention.
Fig. 9 is the ultra-violet absorption spectrum of ligand and complex provided by the present invention 1,2 in methylene chloride under room temperature.
Figure 10 is Solid fluorescene spectrum (λ of the complex 1,2 provided by the present invention at 298Kex=365nm).
Figure 11 is Solid fluorescene spectrum (λ of the complex 1,2 provided by the present invention at 77Kex=365nm).
Figure 12 is CIE diagram provided by the present invention.
Figure 13 is the HOMO-LUMO energy diagram of complex 1-2 provided by the present invention.
Figure 14 is thermal weight loss (TGA) curve of complex 1,2 provided by the present invention.
Specific embodiment
The principles and features of the present invention are described below, and illustrated embodiment is served only for explaining the present invention, is not intended to
It limits the scope of the invention.
Specific embodiment
Instrument and reagent
Nuclear Magnetic Resonance: U.S.'s Unity Varian-600MHz Nuclear Magnetic Resonance；
Fluorescence Spectrometer: U.S.'s PE company LS-55 type Fluorescence Spectrometer；
Ultraviolet spectrometer: U.S.'s PE company Lambda35 type ultraviolet-visible spectrophotometer；
Thermogravimetric, differential thermal analyzer: Perkin-Elmer company, U.S. Diamond TG/DTA type；
Mass spectrograph: Matrix-Assisted Laser Desorption Ionization Time of Flight (MALDI-TOF MS)；
Elemental analyser: German Elementar company Vario Micro Cube elemental analyser；
Crystal diffraction instrument: MAR CCD 165nm crystal diffraction instrument
Test solvent is all from Shanghai Shen Shi chemical industry Trade Co., Ltd., and purity is AR.
THF through sodium silk predrying, be heated to reflux to indicator benzophenone it is blue after steam, magnesium rod is with dilute
Salt acid soak removes surface oxide layer.
Experimental drug is purchased from Aladdin, and purity is AR.
1, the synthesis of complex 1-2
1.1, the synthesis of complex 1
Diphenyl -8- quinolyl phosphine (150mg, 0.48mmol) and cuprous iodide (91.42mg, 0.48mmol) are added
In 20mL methylene chloride, masking foil is wrapped, is protected from light is stirred to react 3h under nitrogen protection, then is added under nitrogen flowing into reaction
Triphenylphosphine (125.9mg, 0.48mmol) stops after the reaction was continued 2h.It is solid to obtain yellow for solvent evaporated after solution is filtered
Body.Obtained product is dissolved in 20mL methylene chloride/acetonitrile (v/v=1:2) in the mixed solvent recrystallization, is finally obtained yellowish
Color crystal 1 (239.02mg, 65%).1H NMR(400MHz,CDCl3): δ=8.87 (s, 1H), 8.24 (d, J=8Hz, 1H),
7.94 (d, J=8Hz, 1H), 7.73 (t, J=8Hz, 1H), 7.60 (t, J=8Hz, 1H), 7.40-7.10 (m, 26H)31P NMR
(240MHz,CDCl3): δ=- 6.01, -27.27.C39H31CuINP2Elemental analysis calculated value (%, measured value): C:61.31
(61.15),H:4.01(4.08),N:1.77(1.83).MALDI-TOF MS(m/z)calcd for C39H31CuNP2:
638.1228；found:638.4546.
1.2, the synthesis of complex 2
Diphenyl -8- quinolyl phosphine (150mg, 0.48mmol) and cuprous bromide (68.86mg, 0.48mmol) are added
In 20mL methylene chloride, masking foil is wrapped, is protected from light is stirred to react 3h under nitrogen protection, then is added under nitrogen flowing into reaction
Triphenylphosphine (125.9mg, 0.48mmol) stops after the reaction was continued 2h.It is solid to obtain yellow for solvent evaporated after solution is filtered
Body.Obtained product is dissolved in 20mL methylene chloride/acetonitrile (v/v=1:2) in the mixed solvent recrystallization, is finally obtained yellowish
Color crystal 2 (220.90mg, 67%).1H NMR(400MHz,CDCl3): δ=8.87 (s, 1H), 8.46 (d, J=8Hz, 1H),
8.13 (d, J=4Hz, 1H), 7.83 (s, 1H), 7.69 (s, J=4Hz, 1H), 7.50 (s, 1H), 7.40-7.17 (m, 25H)31P
NMR(240MHz,CDCl3): δ=- 5.18, -26.60.C39H31CuBrNP2Elemental analysis calculated value (%, measured value): C:
64.91(65.14),H:4.51(4.35),N:1.79(1.83).MALDI-TOF MS(m/z)calcd for C39H31CuNP2:
638.1228；found:638.8403.
2, interpretation of result
2.1, nuclear magnetic spectrum
2.1.1, nuclear magnetic resonance spectroscopy
Complex 1,2 is in CDCl3In nucleus magnetic hydrogen spectrum as shown in Fig. 1~2, the nucleus magnetic hydrogen spectrums of two kinds of complexs both from
Diphenyl -8- quinolyl phosphine and triphenylphosphine, the number of hydrogen matches with complex in nuclear-magnetism figure.
2.1.2, nuclear magnetic resonance phosphorus is composed
Complex 1,2 is in CDCl3In phosphorus spectrum as shown in figs. 34, complex 1 is there are two the δ=- 6.01 and -27.27
The signal of phosphorus, the chemical shift of 2 phosphorus of complex is in δ=- 5.18, and -26.60.Wherein the phosphorus of δ=- 6.01 and -5.18 is from two
Phosphorus in phenyl -8- quinolyl phosphine, δ=- 27.27 and -26.60 phosphorus from triphenylphosphine.
2.2, mass spectrum
Complex 1,2 is surveyed using Matrix-Assisted Laser Desorption Ionization Time of Flight (MALDI-TOF MS)
Examination, test result is as shown in Fig. 5~6.It is to have a fragment peak near 638 that two kinds of complexs, which are all in m/z,.The peak is due to matching
It closes object and sloughs and formed after halogen.
2.3, crystal structure
The crystal of two kinds of complexs be all acetonitrile/methylene chloride (v:v=2:1) in the mixed solvent pass through solvent volatilize
What method was turned out, obtained crystal is faint yellow graininess, and crystal data is as shown in table 1, table 2.
The X ray diffractive crystal data of 1 complex 1,2 of table
The part bond distance of 2 complex 1,2 of tableWith bond angle (°) data
For crystal data as shown in table 1~2, two kinds of complexs belong to anorthic system p-1 space group.It is single in complex 1-2
Respectively with 2 P, it is the tetrahedral configuration of high distortion that 1 N and 1 halogen, which is connected, at copper center.N-Cu-P bond angle is
It is 85.33to85.34 °, entirely different with common tetrahedral bond angle, this is because ligand dpq u has the edge at small occlusion angle
Therefore.Cu (1)-P (2) of complex 1, Cu (1)-P (1) bond distanceSlightly larger than the bond distance of complex 2This may be because of the reason of reprimand electronic capability of I is better than Br.But the Cu of two kinds of complexs
(1)-N (1) key is because the difference of halogen but shows opposite as a result, illustrating that the bond distance of Cu (1)-N (1) key can be because halogen be denounceed
The enhancing of electronic capability and reduce.The bond distance of the Cu-I key of complex 1Greater than the key of the Cu-Br key of complex 2
It is longThis is because the van der Waals radius of I is greater than the reason of Br.In 1 and 2 between P-Cu-X plane and quinoline ring
Dihedral angle is respectively 81.06 °/83.85 °；85.42°/80.55°.There is solvent molecule CH in 12Cl2, there are intermolecular hydrogen in 1 and 2
Key, immediate Cl-to-H, I-to-H, Br-to-H distance are respectivelyWithSolid
Under state, in 1-2 packed structures, there are intermolecular C-H ... π interactions between quinoline ring and phenyl ring, wherein immediate C-
To-H distance is respectivelyCH in 12Cl2In H and phenyl ring between there are intermolecular C-H ... π is mutual
Effect, immediate C-to-H distance isThere is also intermolecular C-H ... π phases between phenyl ring and phenyl ring in 1 and 2
Interaction, immediate C-to-H distance are respectivelyAll these intermolecular forces make to cooperate
Object forms 1D chain structure along a, b and c-axis respectively.The crystal structure of complex 1 as shown in fig. 7, the crystal structure of complex 2 such as
Shown in Fig. 8.
2.4, ultraviolet spectra
Complex 1-2 and ligand diphenyl -8- quinolyl phosphine (dpqu), triphenylphosphine (PPh3) at 298K, dichloro
(concentration is 5 × 10 in dichloromethane-5Mol/L ultra-violet absorption spectrum) is as shown in Figure 9.Ligand triphenylphosphine 260nm (ε=
9.7×103M1cm1) and (ε=8.0 × 10 274nm3M1cm1) at have maximum absorption band.Ligand dpq u 335nm (ε=3.1 ×
103M1cm1) at have maximum absorption band, belong to Phenylphosphine, the lone pair electrons in quinoline phosphine in P or N are to transitting to phenyl ring or quinoline
The transition of n → π * of quinoline ring, wherein being also mixed with π → π * transition between phenyl ring and quinoline ring.Complex 1 and 2 286nm (ε=
1.8×103M-1cm-1) and (ε=2.2 × 10 368nm3M-1cm-1) there is maximum absorption band, there is weak absorption tail in 380-400nm
Band is attributable to the charge transtion of copper, halogen to ligand.
2.5, fluorescence spectrum
Complex 1 and 2 is at 298K, and as shown in Figure 10 with the Solid fluorescene spectrum that 365nm is excited, complex 1,2 is distinguished
There is maximum emission peak at 606nm and 620nm.The respective service life is respectively 7.58us and 8.23us.Maximum emission wavelength 1 < 2,
This (I that also puts in order with the field strength of halogen-<Br-) consistent, it means that the electricity of complex 1,2 to shine by halogen to ligand
The influence of lotus transition (XLCT).Such as Figure 11, complex 1,2 is at low temperature 77K, 365nm excitation, respectively at 609nm, 619nm
There is maximum emission peak, the service life is respectively 84.18us and 54.55us.As temperature is down to 77K, the maximum of complex 1 by 298K
Emission peak has a little red shift (3nm), and complex 2 has almost no change.Service life, which is down to 77K by 298K with temperature, apparent increasing
Add (1 order of magnitude), this transmitting of explanation at 77K is from triplet T1 [9], room temperature luminous that there is thermal activation delayed fluorescence
TADF feature.The quantum efficiency of complex 1 and 2 is respectively 6.24% and 2.85%, this is because the N^P in molecule can be with
Cu occurs coordination and forms the enclosed construction with rigidity, the steric configuration of molecule can be made more stable in this way.As shown in figure 12,
Based on room temperature luminous spectrum data, the CIE coordinate of complex 1 is (0.5616,0.436), and the CIE coordinate of complex 2 is
(0.5795,0.4185) is orange light.As far as we know, this is the cuprous halide complex of report hair orange light for the first time.
2.6, molecular frontier orbital energy calculates
As shown in figure 13, complex 1,2 highest occupied molecular orbital(HOMO) (HOMO) are concentrated on respectively on Cu and halogen, and most
The low quinoline moiety for not occupying molecular orbit (LUMO) and then all concentrating on ligand diphenyl -8- quinolyl phosphine, therefore, complex hair
Light is mainly due to the center (X=I, Br) CuX to the energy level transition of ligand diphenyl -8- quinolyl phosphine, that is, (metal+halogen
Element) arrive ligand charge transtion ((M+X) LCT).I, Cu, P in complex 11, P2, the HOMO contribution margin of N is respectively 0.73,
0.12,0.04,0.05 and 0.0006, I, Cu, P in complex 21, P2, the HOMO contribution margin of N is respectively 0.64,0.20,0.06,
0.07 and 0.002.Meanwhile the T of complex 1,2 is calculated1To S1Energy gap be respectively 0.0232eV and 0.0119eV.Due to
The T of two kinds of complexs1To S1Energy gap is smaller and much smaller than 0.37eV.And the service life with temperature by 77K rise to 298K have it is bright
Aobvious reduction, therefore may determine that two kinds of complexs shine all is hot activation retardance fluorescence (TADF).
2.7, thermogravimetic analysis (TGA)
Thermal weight loss (TGA) curve of complex 1,2 is as shown in figure 14, is tested in the environment of nitrogen atmosphere.Cooperation
Object 2 is 2 step weightlessness processes, and weightlessness starts from 260 DEG C, and weightless ratio is 35%.Its weightless part mostlys come from complex mistake
Triphenylphosphine is removed, step 2 weightlessness starts from 350 DEG C, and weightless ratio is 40%, and weightless part mostlys come from complex and loses
Diphenyl -8- quinolyl phosphine.The TGA curve of complex 1 shows as three step weightlessness processes, and first step weightlessness occurs to lose at 100 DEG C
Weight ratio is 6%, it can be concluded that coming from the weightless platform for not drying complete water in sample.First step weightlessness hair
Raw at 263 DEG C, weightless ratio is 36%, and step 3 weightlessness starts from 382 DEG C, and weightless ratio is 20%, and weightless part is mainly come
Diphenyl -8- quinolyl phosphine is lost from complex.The result shows that complex 1 and complex 2 all have good thermal stability.
The present invention has synthesized 2 kinds of novel mixed matching Cu (I) and has matched using diphenyl -8- quinolyl phosphine and triphenylphosphine as ligand
Close object, and to by nuclear-magnetism (1H NMR,13C NMR,31P NMR), mass spectrum, elemental analysis and single crystal diffraction carry out its structure
Confirmation.Its luminescent properties and thermal stability are studied with ultraviolet and fluorescence spectrum instrument and thermogravimetric analyzer.Two kinds of cooperations
There is fluorescent emission in orange light region under object solid-state, wherein 1,2 solid fluorescence quantum efficiency is respectively 6.24% and 2.85%,
It is the cuprous halide complex of report hair orange light for the first time.Molecule frontier orbit calculates discovery the type complex T1To S1Energy level difference
0.0232eV and 0.0119eV respectively is much smaller than 0.37eV, illustrates that such complex shines and belongs to hot activation retardance fluorescence.
It shines and is mainly derived from MLCT and XLCT.Orange light light luminescent material be can be used as applied to OLED.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (7)
1. diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex, which is characterized in that general structure is as follows:
Wherein, X is Br or I.
2. the synthetic method of diphenyl -8- quinolyl phosphine and triphenylphosphine mixture cuprous halide complex, which is characterized in that including
Following steps:
Wherein, X is Br or I.
3. a kind of diphenyl -8- quinolyl phosphine according to claim 1 and triphenylphosphine mixture cuprous halide complex
Using, it is characterised in that: as fluorescent material.
4. the application of diphenyl -8- quinolyl phosphine according to claim 3 and triphenylphosphine mixture cuprous halide complex,
It is characterized by: as thermal activation delayed fluorescence material.
5. diphenyl -8- quinolyl phosphine according to claim 3 or 4 is answered with triphenylphosphine mixture cuprous halide complex
With, it is characterised in that: as orange light fluorescent material.
6. a kind of diphenyl -8- quinolyl phosphine according to claim 1 and triphenylphosphine mixture cuprous halide complex
Using, it is characterised in that: as Organic Light Emitting Diode material.
7. a kind of OLED device includes at least organic luminous layer, it is characterised in that: the material of the organic luminous layer is selected from right
It is required that diphenyl -8- quinolyl phosphine provided by 1 and any one in triphenylphosphine mixture cuprous halide complex or two kinds
Mixing.
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2019
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Non-Patent Citations (2)
| Title |
|---|
| LI-PING LIU ET AL.: "Near-saturated red emitters: four-coordinate copper(I) halide complexes containing 8-(diphenylphosphino)quinoline and 1-(diphenylphosphino)naphthalene ligands", 《DALTON TRANS.》 * |
| 齐磊: "二苯基联苯、喹啉和芴基卤化铜(I)配合物的合成与表征", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111548368A (en) * | 2020-05-28 | 2020-08-18 | 安徽大学 | Copper nanocluster with high stability and near-infrared phosphorescence and preparation method thereof |
| CN111548368B (en) * | 2020-05-28 | 2023-02-03 | 安徽大学 | Copper nanocluster with high stability and near-infrared phosphorescence and preparation method thereof |
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