CN108752382A - The double phosphine three-fold coordination cuprous halide complexs of terphenyl and synthetic method and application - Google Patents
The double phosphine three-fold coordination cuprous halide complexs of terphenyl and synthetic method and application Download PDFInfo
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- CN108752382A CN108752382A CN201810699734.1A CN201810699734A CN108752382A CN 108752382 A CN108752382 A CN 108752382A CN 201810699734 A CN201810699734 A CN 201810699734A CN 108752382 A CN108752382 A CN 108752382A
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- terphenyl
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- phosphine
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 46
- 150000004820 halides Chemical class 0.000 title claims abstract description 29
- 238000010189 synthetic method Methods 0.000 title claims abstract description 13
- 239000003446 ligand Substances 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 11
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims abstract description 7
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims abstract description 6
- BCIDDURGCAHERU-UHFFFAOYSA-N 1,2-dibromo-4,5-dimethylbenzene Chemical class CC1=CC(Br)=C(Br)C=C1C BCIDDURGCAHERU-UHFFFAOYSA-N 0.000 claims abstract description 5
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000007116 intermolecular coupling reaction Methods 0.000 claims abstract description 4
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 16
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical compound C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical group [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 2
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 230000003111 delayed effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 230000007246 mechanism Effects 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- -1 phosphine compound Chemical class 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000006862 quantum yield reaction Methods 0.000 description 3
- 238000000935 solvent evaporation Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000004847 absorption spectroscopy Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000003775 Density Functional Theory Methods 0.000 description 1
- 206010023126 Jaundice Diseases 0.000 description 1
- 208000032443 Masked facies Diseases 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 210000002659 acromion Anatomy 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 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
- 239000007788 liquid Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 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
- 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
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The present invention relates to the double phosphine three-fold coordination cuprous halide complexs of terphenyl and synthetic method and applications, belong to luminescent material technical field.The present invention is with 1,2 dimethyl -4,5- dibromobenzenes are starting material, the double lithium reagents of terphenyl are synthesized by intermolecular coupling reaction, then nucleophilic substitution synthetic ligands dbdp occurs with diphenyl phosphine chloride, the target product for reacting the synthesis present invention as ligand with cuprous halide using dbdp again, finally characterizes the structure of target product with luminescent properties.The result shows that at normal temperatures, the double phosphine three-fold coordination cuprous iodide complex green lights of solid-state terphenyl, the double phosphine three-fold coordination cuprous bromide complexs of terphenyl and the double phosphine three-fold coordination CuCl-compounds of terphenyl turn to be yellow green lights.Synthetic method of the present invention is simple, easy to operate, and target product obtained has the luminescent lifetime of Microsecond grade in room temperature, illustrates that target product luminescence mechanism is thermal activities delayed fluorescence, potential that electroluminescent material is used as to be applied to OLED.
Description
Technical field
The invention belongs to luminescent material technical fields, it is more particularly related to the double phosphine three-fold coordination halogenations of terphenyl
Cuprous complex and synthetic method and application.
Background technology
Regulate and control the structure and configuration of copper (I) complex by selecting rigid ligand, the group with steric hindrance, is to close
At the key of High Efficiency Luminescence copper (I) complex.When P atoms in biphosphine ligand are connect with aromatic rings, compound is shown well
Coordination ability can form stable complex with Cu (I).It is put down studies have shown that ligand steric hindrance can form three-fold coordination when larger
Face rigidity Cu (I) complex, the non-radiative decay caused by " Jahn-Teller distortions " when can effectively inhibit excitation state
Process increases substantially luminous efficiency.2011, Japanese chemists Osawa etc. reported highly effective green light three-fold coordination (I) cooperation
Object, the Organic Light Emitting Diode external quantum efficiency (EQE) assembled with the complex is more than 20%.Currently, three-fold coordination copper (I) is matched
The report for closing object is seldom.Therefore, the larger bidentate phosphine compound of design synthesizing new steric hindrance is for synthesizing three-fold coordination Cu
(I) compound has important research significance.
Invention content
In view of the problems of the existing technology, the purpose of the present invention is to provide the double phosphine three-fold coordination cuprous halides of terphenyl to match
Close object and synthetic method and application.Present invention design has synthesized terphenyl bidentate phosphine ligands (4,4', 4 ", 5,5', 5 "-pregnancy
Base-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands), then it is coordinated and closes with CuX (X=I, Br, Cl)
At a series of cuprous complex of neutrality of monokaryon three-fold coordinations, and utilize nuclear-magnetism, infrared, monocrystalline XRD, mass spectrum, ultraviolet, glimmering
Light, thermogravimetic analysis (TGA) etc. are tested characterization to the structure and photophysical property of complex.
In order to realize that above-mentioned first purpose of the present invention, the present invention adopt the following technical scheme that：
The double phosphine three-fold coordination cuprous halide complexs of terphenyl of the present invention, empirical formula are：C48H44CuXP2, described
Complex is anorthic system, and P-1 space groups, crystal color is colourless, wherein：Any one of described X=I, Br or Cl, institute
The molecular structural formula of the double phosphine three-fold coordination cuprous halide complexs of terphenyl is stated as shown in following formula one：
Further, when X=I described in above-mentioned technical proposal, the complex is specially the double phosphine three-fold coordinations of terphenyl
Cuprous iodide complex, empirical formula are：C48H44CuIP2, molecular weight 873.22, cell parameter Z=2, the complex are monokaryon three-fold coordination structure, with
Copper (I) atom is geometric center, forms plane triangle.The complex forms one-dimensional (1-D) banded structure along a axis.
Further, when X=Br described in above-mentioned technical proposal, the complex is specially the double phosphine three-fold coordinations of terphenyl
Cuprous bromide complex, empirical formula are：C48H44CuBrP2, molecular weight 996.07, cell parameter Z=2, the complex are monokaryon three-fold coordination knot
Structure forms plane triangle, and the structure of the complex is containing there are two CH using copper (I) atom as geometric center2Cl2Solvent point
Son.The complex forms one-dimensional (1-D) banded structure along a axis.
Further, when X=Cl described in above-mentioned technical proposal, the complex is specially the double phosphine three-fold coordinations of terphenyl
CuCl-compound, empirical formula are：C48H44CuClP2, molecular weight 781.76, cell parameter Z=2, the complex are formed one-dimensional (1-D) along c-axis
Banded structure.
Another object of the present invention is to provide the double phosphine three-fold coordination cuprous halide complex (targets of terphenyl described above
Product) synthetic method, described method includes following steps：
By terphenyl bidentate phosphine ligands 4,4', 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 " -
Two (diphenylphosphine) ligands (dbdp) and cuprous halide are added in q. s. methylene chloride, are filtered after reacting 5h, are depressurized outstanding dry molten
Agent obtains pistac solid, then the pistac solid is dissolved in the mixed solvent being made of dichloromethane and ethyl alcohol
In, solvent is volatilized again at room temperature, obtains clear crystal, the i.e. double phosphine three-fold coordination cuprous halide complexs of the terphenyl.
Further, 4,4' described in above-mentioned technical proposal, 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-three connection
Phenyl) -2,2 " molar ratio of-two (diphenylphosphine) ligands and cuprous halide is 1：1.
Further, 4,4' described in above-mentioned technical proposal, 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-three connection
Phenyl) -2,2 " proportioning of-two (diphenylphosphine) ligands and dichloromethane is preferably 0.21mmol：20mL.
Further, the volume ratio of the in the mixed solvent dichloromethane and ethyl alcohol described in above-mentioned technical proposal is preferably 3：
1。
Further, 4,4' described in above-mentioned technical proposal, 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-three connection
Phenyl) -2,2 "-two (diphenylphosphine) ligands (dbdp) are specifically prepared, include the following steps with the following method：
With 1,2- dimethyl -4,5- dibromobenzenes for raw material, by being given birth to by intermolecular coupling reaction with reagent n-butyllithium
Nucleophilic substitution synthesising target compound 4,4', 4 ", 5,5' occurs at the double lithium reagents of terphenyl, then with diphenyl phosphine chloride,
5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands.
4,4' described above, 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenyl
Phosphine) ligand synthetic route as shown in formula two：
The synthetic route of the double phosphine three-fold coordination cuprous halide complexs of terphenyl described above is as shown in formula three：
A further purpose of the present invention is to provide the double phosphine three-fold coordination cuprous halides of target product terphenyl described above to match
The application for closing object can be used as electroluminescent material group dress OLED.
A kind of assembling OLED electroluminescent materials, the luminescent material are the double phosphines of present invention terphenyl described above
Three-fold coordination cuprous halide complex.
Compared with prior art, the present invention has the advantages that：
(1) yield of the method for the present invention synthesis target product is high, up to 80%, in addition, synthetic method of the present invention is simple, easy
Operation does not need expensive instrument and equipment, is conducive to industrialization；
(2) present invention synthesizes three with 1,2 dimethyl -4,5- dibromobenzene for starting material by intermolecular coupling reaction
Then nucleophilic substitution occurs with diphenyl phosphine chloride and synthesizes terphenyl bidentate phosphine ligands 4,4' for the double lithium reagents of benzene, and 4 ", 5,
5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligand dbdp, then using dbdp as ligand
The target product that the synthesis present invention is reacted with cuprous halide, finally characterizes the structure of target product with luminescent properties,
The result shows that at normal temperatures, the double phosphine three-fold coordination cuprous iodide complex green lights of solid-state terphenyl, the double phosphine three-fold coordinations of terphenyl
Cuprous bromide complex and the double phosphine three-fold coordination CuCl-compounds jaundice green lights of terphenyl, solid-state maximum absolute quantum efficiency
(PLQY) it is 5.43%；
(3) singlet and the energy difference of triplet state are smaller (less than 0.37 in the solid state for target product produced by the present invention
EV), while in room temperature there is the luminescent lifetime of Microsecond grade, illustrate that target product luminescence mechanism is thermal activities delayed fluorescence, in addition
The present invention also shows that the big terphenyl structure of steric hindrance helps to synthesize monokaryon three-fold coordination copper (I) complex, potential as electricity
Electroluminescent material is applied to OLED.
Description of the drawings
Fig. 1 is the 4,4', 4 ", 5,5' that the embodiment of the present invention 1 synthesizes, 5 "-hexamethyls-(1,1':2', 1 "-terphenyl)-
2,2 "-two (diphenylphosphine) ligand dbdp are in CDCl3In nuclear magnetic resonance spectroscopy；
Fig. 2 is the double phosphine three-fold coordination cuprous iodide complexs of terphenyl of the synthesis of the embodiment of the present invention 2 in CDCl3In nuclear-magnetism
Resonate hydrogen spectrum；
Fig. 3 is the double phosphine three-fold coordination cuprous bromide complexs of terphenyl of the synthesis of the embodiment of the present invention 3 in CDCl3In nuclear-magnetism
Resonate hydrogen spectrum；
The double phosphine three-fold coordination CuCl-compounds of terphenyl that Fig. 4 embodiment of the present invention 4 synthesizes are in CDCl3In nuclear-magnetism it is total
The hydrogen that shakes is composed；
(a), (b), (c) distinguish complex 1, complex 2, complex made from the above embodiment of the present invention 2~4 in Fig. 5
3 crystal structure figure；
Fig. 6 is the infared spectrum of ligand dbdp and complex 1~3；
When Fig. 7 is 298K, ligand dbdp and complex 1~3 are in CH2Cl2In uv-visible absorption spectroscopy figure；
Fig. 8 (a), (b) are respectively solid fluorescence transmitting collection of illustrative plates of the complex 1~3 respectively in 293K and 77K；
Fig. 9 is that the CIE diagram of complex 1~3 is composed；
Figure 10 is thermal weight loss (TGA) curve graph of complex 1~3.
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
Process, property or component defined by being not limited to, because these embodiments and other descriptions are just for the sake of signal
Property illustrates certain aspects of the present disclosure.In fact, this field or those skilled in the relevant art can obviously implement the present invention
The various changes that mode 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
The effective digital of announcement and by it is conventional round up method by obtain.
Embodiment 1
The 4,4' of the present embodiment, 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenyl
Phosphine) ligand (dbdp) synthetic method, include the following steps：
The three-neck flask that will 1,2- dimethyl -4,5- dibromobenzene (1g, 3.81mmol) be housed is added 20 under vacuum
ML THF, cool the temperature to -78 DEG C, be slowly dropped into 2.02mL n-BuLis hexane solution (2.5mol/L, 5.06
Mmol), -78 DEG C of temperature is kept, diphenyl phosphine chloride (0.56g, 2.53mmol) is added after being stirred to react 1h, continues to stir 2h,
It then heats to room temperature, stirs and 15mL water quenchings are added after 12h go out reaction, organic phase is obtained by extraction with dichloromethane, is steamed after drying
Organic solvent is gone to obtain yellow oily liquid, then with petroleum ether：Dichloromethane=4:1 (volume ratio) is that solvent passes through column
Chromatography method obtains white solid product 0.55g, yield 30.5%.
IR(KBr,ν/cm-1) test result is as follows：3070,2920,2843,1586,1467,1446,1428,1100,
748,697.
1H NMR (600MHz, CDCl3) test result is as follows：δ:7.42~7.30 (m, 12H), 7.25~7.23 (m,
4H), 7.15~7.10 (m, 6H), 6.86 (s, 2H), 6.53 (s, 2H), 2.08 (s, 6H), 2.02 (s, 6H), 2.00 (s, 6H)
.13C NMR (150MHz, CDCl3), δ=146.37,146.10,139.74,139.64,138.38,138.28,137.26,
137.20,136.90,134.96,134.27,134.11,132.86,132.72,128.47,128.34,128.28,
128.05,128.00,127.44,19.52,19.41,19.24.
31P NMR(240MHz,CDCl3) test result is as follows：δ=- 19.19.LC-MS TOF (m/z):Anal.Calcd.
for[M–Me–2Ph–H]+:513.1979；Found:513.1452；Anal.Calcd.for[M–4Me–Ph+H]+:
550.1901；Found:550.2353；Anal.Calcd.for[M–5Me+H]+:611.2136；Found:611.2191.
Embodiment 2
The double phosphine three-fold coordination cuprous iodide complexs (complex 1) of the terphenyl of the present embodiment, prepare with the following method and
At including the following steps：
20mL dichloros are added in the dbdp (143mg, 0.21mmol) and cuprous iodide (0.21mmol) that embodiment 1 is synthesized
It in methane, is filtered after reacting 5h, depressurizes outstanding dry solvent and obtain pistac solid.Pistac solid is dissolved in 10mL bis- again
Chloromethanes/ethyl alcohol (V:V=3：1) in the mixed solvent finally obtains clear crystal using solvent evaporation method at room temperature, i.e. institute
The complex 1 stated, yield 80%.
The relevant test data of the complex 1 of above-mentioned synthesis is as follows：
1H NMR(600MHz,CDCl3) test result is as follows：δ:7.96~7.91 (m, 4H), 7.45~7.42 (m, 6H),
7.24~7.20 (m, 2H), 7.11~7.05 (m, 6H), 6.94~6.92 (m, 2H), 6.84~6.79 (m, 4H), 6.41 (s,
2H),2.21(s,6H),2.15(s,6H),2.00(s,6H).
31P NMR(240M,CDCl3) test result is as follows：δ:-15.60(s).Anal.Calcd for C48H44ICuNP2:
C,66.02；H,5.08；Found:C,66.13；H,5.11.MS(MALDI-TOF):m/z calcd for[C42H39CuIP2],
796.1720,found:795.9119.
Embodiment 3
The double phosphine three-fold coordination cuprous bromide complexs (complex 2) of the terphenyl of the present embodiment, prepare with the following method and
At including the following steps：
20mL dichloros are added in the dbdp (143mg, 0.21mmol) and cuprous bromide (0.21mmol) that embodiment 1 is synthesized
It in methane, is filtered after reacting 5h, depressurizes outstanding dry solvent and obtain pistac solid.Pistac solid is dissolved in 10mL bis- again
Chloromethanes/ethyl alcohol (V:V=3：1) in the mixed solvent finally obtains clear crystal using solvent evaporation method at room temperature, i.e. institute
The complex 2 stated, yield are：78%, the relevant test data of the complex 2 is as follows：
1H NMR(600MHz,CDCl3) test result is as follows：δ:7.94 (s, 4H), 7.44~7.40 (m, 6H), 7.22~
7.20 (m, 2H), 7.09~7.04 (m, 6H), 6.93~6.90 (m, 2H), 6.78~6.75 (m, 4H), 6.48~6.47 (m,
2H),2.21(s,6H),2.15(s,6H),2.00(s,6H).
31P NMR(240M,CDCl3) test result：δ:-15.42(s).Anal.Calcd for C48H44BrCuNP2:C,
69.77；H,5.37；Found:C,69.81；H,5.42.MS(MALDI-TOF):m/z calcd for[C42H39CuBrP2],
747.1006,found:747.1121.
Embodiment 4
The double phosphine three-fold coordination CuCl-compounds (complex 3) of the terphenyl of the present embodiment, prepare with the following method and
At including the following steps：
20mL dichloros are added in the dbdp (143mg, 0.21mmol) and stannous chloride (0.21mmol) that embodiment 1 is synthesized
It in methane, is filtered after reacting 5h, depressurizes outstanding dry solvent and obtain pistac solid.Pistac solid is dissolved in 10mL bis- again
Chloromethanes/ethyl alcohol (V:V=3：1) in the mixed solvent finally obtains clear crystal using solvent evaporation method at room temperature, i.e. institute
The complex 3 stated, the relevant test data of yield 75%, the complex 3 are as follows：
1H NMR(600MHz,CDCl3) test result is as follows：δ:7.96~7.92 (m, 4H), 7.43~7.42 (m, 6H),
7.23~7.20 (m, 2H), 7.08~7.03 (m, 6H), 6.92~6.90 (m, 2H), 6.78~6.74 (m, 4H), 6.47 (s,
2H),2.20(s,6H),2.14(s,6H),2.00(s,6H).
31P NMR(240M,CDCl3) test result：δ:-14.51(s).Anal.Calcd for C48H44BrCuNP2:C,
73.74；H,5.64；Found:C,73.81；H,5.71.MS(MALDI-TOF):m/z calcd for[C42H39CuClP2],
703.1512,found:703.2214.
Complex 1 made from the above embodiment of the present invention 2~4, complex 2, complex 3 crystal structure figure respectively such as
(a), (b), (c) are shown in Fig. 5.
The X-ray single crystal diffraction tables of data of 1 complex 1~3 of table
The crystal structure bond angle (deg) of 2 complex 1~3 of table and bond distanceData
The crystal structure figure of above-mentioned complex 1~3 is as shown in Figure 5.The structure of complex 2 is containing there are two CH2Cl2Solvent point
Son.Crystallographic data and bond distance and bond angle provide in tables 1 and 2 respectively.Show complex 1, cooperation according to crystal structure
Object 2 is monokaryon three-fold coordination structure, using copper (I) atom as geometric center, forms plane triangle.The pericentral angle Cu (I)
The sum of degree has monokaryon three-fold coordination Cu (I) halide of bidentate ligand (359.66 °) similar with report, respectively
359.32 °, 359.70 ° and 359.39 °.As listed in table 2, the Cu-X distances of three kinds of complexs of synthesis with X Van der Waals half
The increase of diameter and increase.In addition, it is observed that intramolecular hydrogen bond in three kinds of complexs, apart from nearest IH,
Bond distance between BrH and ClH be respectively 3.111,2.774 andIn the solid state, complex 1 is shown
Intermolecular C-H π interaction between phenyl ring and methyl in terphenyl, wherein immediate C to H away from
From being 2.831, and the H-H distances nearest between phenyl ring and methyl that are connected with phosphorus are2 company of showing of complex
The intermolecular C-H π interactions being connected between two phenyl ring on phosphorus, wherein immediate C-H distances areThe intermolecular C-H π of complex 2 interact and can be observed between the phenyl ring that P atoms are connected,
Wherein immediate C-H distances areThe intermolecular C-H π interactions of complex 3 can be in terphenyl
It is observed between the intermediate phenyl ring and methyl of group, wherein immediate C-H distances areResearch it is also shown that it is all this
A little intermolecular forces all make complex 1,2 along a axis, and complex 3 forms one-dimensional (1-D) banded structure along c-axis.
Fig. 6 is the infared spectrum of ligand dbdp and complex 1~3, is tested using KBr tablettings, it will be appreciated from fig. 6 that
High frequency region 3050cm-1Absorption band is aromatic ring c h bond stretching vibration peak；1586,1467 and 1446cm-1Absorption band is aromatic ring frame
Stretching vibration peak；1100cm-1Absorption band is aromatic ring C-H in-plane bending vibrations peak；Low frequency range 748 and 697cm-1Absorption band is single
Replace aromatic ring C-H out-of-plane bending vibrations peak.Pass through comparison, it can be seen that the infrared signature absorption peak of ligand and complex does not have
Significant change illustrates to form the structure that complex contains ligand itself.
Fig. 7 is ligand dbdp and complex 1~3 in CH2Cl2In uv-visible absorption spectroscopy figure, dbdp and cooperation
The concentration of object 1~3 is 8 × 10-5M.As shown in Figure 7, ligand dbdp is in (ε=1.33 × 10 283nm4M-1cm-1) at show
Wide and strong bands of a spectrum, this is the feature ultraviolet absorption peak of phenyl phosphine compound.This absorption peak is attributable to mixed n → π *
The collective effect of electronics transfer and π → π * electronics transfers.N → π * electronics transfers refer to electronics from the lone pair electrons track on phosphorus
The empty antibonding π * tracks being changed on phenyl ring or cyclohexyl biphenyl, π → π * electronics transfers refer to the internal transitions from phenyl ring or cyclohexyl biphenyl
Or the electron transition from cyclohexyl biphenyl to phenyl ring.Three complexs have similar wide absorption peak at 280~287nm, meanwhile, match
Closing object, there are one relatively weak low energy absorption peaks, this absorption to be attributable to metallic copper to ligand at 330~360nm
Charge transtion, halogen to ligand charge transtion and match internal charge transtion.
Optical physics tables of data of 3 complex 1~3 of table in solid-state
* indicate that emission peak is acromion or weak peak；aIndicate maximum emission wavelength；bLuminescent lifetime, experimental error are ± 5%；c
Solid-state absolute quantum yield, experimental error are ± 5%；dResult of calculation (the S obtained by the structure that X-ray analysis determines1With
T1Energy level and S1And T1Between energy gap).
Fig. 8 is that solid fluorescence of the complex 1~3 respectively in 293K and 77K emits collection of illustrative plates.When table 3 is 293K and 77K,
Corresponding maximum emission wavelength (the λ of three complexsmax), fluorescence lifetime (τ), absolute quantum yield (Φ) and according to mono-crystalline structures
The Density function theory (TDDFT) of data.In 293K, 1 green light of complex, maximum emission wavelength 493nm matches
Object 2 and 3 is closed to turn to be yellow green light, maximum emission wavelength is respectively 527 and 533nm, wherein at room temperature, complex 1~3 it is absolute
Quantum yield ΦPLNo more than 5.43%.This wide and non-structured emission band is shown has charge in transmitting excitation state
Transfer.With the reduction of coordination field intensity, the energy gap of d tracks also reduces, this also has led to the MLCT energy levels of bigger.?
Observe that the transmitting die-away time of complex 1~3 is 7.23~415.91 μ s when 293K.Than 1 to 3 quantity of 77K short life
Grade, shows to produce TADF (hot activation delayed fluorescence).PL data when based on 293K, the international lighting committee of complex 1~3
Member's meeting (CIE) color coordinates is respectively (0.2246,0.3898), and (0.3172,0.4138) and (0.3663,0.5151) such as schemes
Shown in 9.
In 77K, the maximum emission peak of complex 1~3 is respectively 542,537 and 544nm.The transmitting of complex 1~3
Red shift has occurred in bands of a spectrum at low temperature, because of low-lying excitation state (T1) account at low temperature it is leading.Due to including vibration and rotation
Structure change inside inhibits excited energy vibration relaxation, the emission band of complex 1~3 that blue shift occurs in low temperature.
Moreover, T when low temperature1Excitation state accounts for leading.Table 3 summarizes the singlet energy level (S of complex 1~31), triplet (T1)
With the energy level difference Δ E (S of the two1-T1).The S of complex 1~31And T1Between energy level difference it is very small (0.0608~
0.1271eV), further prove that complex 1~3 produces TADF.And the complex electronics that the present invention synthesizes is distributed main office
The phenyl ring for being limited to the phenyl ring in ligand dbdp in terphenyl and being connected with phosphorus, these show that complex shines and are derived from MLCT,
XLCT and IL transition.
Since the good thermal stability of complex is particularly important for the application of OLED, lead under a nitrogen atmosphere
Cross the initial decomposition temperature (T that TGA determines complex 1~3dec), since TGA curves (as shown in Figure 10), all cooperations
Object all shows good thermal stability, TdecRanging from 322~392 DEG C of value.Cooperation is observed between 392~600 DEG C
1~3 weightlessness about 78~91% of object, this may be due to eliminating dbdp ligands.These data illustrate these three complex conducts
Luminescent layer guest materials is applicable to vacuum steaming and crosses method assembling OLED device.
Claims (10)
1. the double phosphine three-fold coordination cuprous halide complexs of terphenyl, it is characterised in that：Its empirical formula is：C48H44CuXP2, the cooperation
Object is anorthic system, and P-1 space groups, crystal color is colourless, wherein：Any one of described X=I, Br or Cl, described three
The molecular structural formula of the double phosphine three-fold coordination cuprous halide complexs of benzene is as shown in following formula one：
2. the double phosphine three-fold coordination cuprous halide complexs of terphenyl described in claim 1, it is characterised in that：When the described X=I,
The complex is specially the double phosphine three-fold coordination cuprous iodide complexs of terphenyl, and empirical formula is：C48H44CuIP2, molecular weight is
873.22, cell parameterZ=2, it is described
Complex is monokaryon three-fold coordination structure, using copper (I) atom as geometric center, forms plane triangle.The complex is along a axis shapes
At one-dimensional (1-D) banded structure.
3. the double phosphine three-fold coordination cuprous halide complexs of terphenyl described in claim 1, it is characterised in that：When the described X=Br,
The complex is specially the double phosphine three-fold coordination cuprous bromide complexs of terphenyl, and empirical formula is：C48H44CuBrP2, molecular weight is
996.07, cell parameter Z
=2, the complex is monokaryon three-fold coordination structure, using copper (I) atom as geometric center, formation plane triangle, and described match
The structure of object is closed containing there are two CH2Cl2Solvent molecule.The complex forms one-dimensional (1-D) banded structure along a axis.
4. the double phosphine three-fold coordination cuprous halide complexs of terphenyl described in claim 1, it is characterised in that：When the described X=Cl,
The complex is specially the double phosphine three-fold coordination CuCl-compounds of terphenyl, and empirical formula is：C48H44CuClP2, molecular weight is
781.76, cell parameter Z
=2, the complex forms one-dimensional (1-D) banded structure along c-axis.
5. the synthetic method of the double phosphine three-fold coordination cuprous halide complexs of Claims 1 to 4 any one of them terphenyl, feature
It is：By terphenyl bidentate phosphine ligands 4,4', 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two
(diphenylphosphine) ligand (dbdp) and cuprous halide are added in q. s. methylene chloride, are filtered after reacting 5h, are depressurized and are hanged dry solvent
Pistac solid is obtained, then the pistac solid is dissolved in the in the mixed solvent being made of dichloromethane and ethyl alcohol,
Solvent is volatilized again at room temperature, obtains clear crystal, the i.e. double phosphine three-fold coordination cuprous halide complexs of the terphenyl.
6. the synthetic method of the double phosphine three-fold coordination cuprous halide complexs of terphenyl according to claim 5, it is characterised in that：
The 4,4', 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands and halogen
It is 1 to change cuprous molar ratio：1.
7. the synthetic method of the double phosphine three-fold coordination cuprous halide complexs of terphenyl according to claim 5, it is characterised in that：
The 4,4', 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands and two
The proportioning of chloromethanes is 0.21mmol：20mL.
8. the synthetic method of the double phosphine three-fold coordination cuprous halide complexs of terphenyl according to claim 5, it is characterised in that：
The 4,4', 4 ", 5,5', 5 "-hexamethyls-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands
(dbdp) it is specifically prepared, includes the following steps with the following method：
With 1,2- dimethyl -4,5- dibromobenzenes for raw material, by generating three by intermolecular coupling reaction with reagent n-butyllithium
The double lithium reagents of biphenyl, then nucleophilic substitution synthesising target compound 4,4', 4 ", 5,5', 5 "-six occurs with diphenyl phosphine chloride
Methyl-(1,1':2', 1 "-terphenyl) -2,2 "-two (diphenylphosphine) ligands.
9. the application of the double phosphine three-fold coordination cuprous halide complexs of Claims 1 to 4 any one of them terphenyl, feature exist
In：It can be used as electroluminescent material group dress OLED.
10. a kind of assembling OLED electroluminescent materials, it is characterised in that：The luminescent material is any one of Claims 1 to 4
The double phosphine three-fold coordination cuprous halide complexs of the terphenyl.
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| CN111848676A (en) * | 2020-08-21 | 2020-10-30 | 郑州大学 | Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof |
| CN111892628A (en) * | 2020-08-21 | 2020-11-06 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
| CN115819461A (en) * | 2022-11-02 | 2023-03-21 | 黄河三角洲京博化工研究院有限公司 | Novel bidentate phosphine ligand and preparation method thereof |
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| CN111848676A (en) * | 2020-08-21 | 2020-10-30 | 郑州大学 | Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof |
| CN111892628A (en) * | 2020-08-21 | 2020-11-06 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
| CN111892628B (en) * | 2020-08-21 | 2021-05-11 | 郑州大学 | Luminescent copper (I) complex based on pyridoimidazole diphosphine derivative and preparation method thereof |
| CN111848676B (en) * | 2020-08-21 | 2021-06-29 | 郑州大学 | Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof |
| CN115819461A (en) * | 2022-11-02 | 2023-03-21 | 黄河三角洲京博化工研究院有限公司 | Novel bidentate phosphine ligand and preparation method thereof |
| CN115819461B (en) * | 2022-11-02 | 2024-06-07 | 黄河三角洲京博化工研究院有限公司 | Bidentate phosphine ligand and preparation method thereof |
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