CN111848676B - Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof - Google Patents
Luminescent copper compound based on benzimidazole diphosphine ligand and preparation method thereof Download PDFInfo
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- 150000001880 copper compounds Chemical class 0.000 title claims abstract description 96
- 239000005749 Copper compound Substances 0.000 title claims abstract description 86
- 239000003446 ligand Substances 0.000 title claims abstract description 80
- IBVKRSGLETVWOE-UHFFFAOYSA-N P.P.N1=CNC2=C1C=CC=C2 Chemical compound P.P.N1=CNC2=C1C=CC=C2 IBVKRSGLETVWOE-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- 229940126062 Compound A Drugs 0.000 claims description 16
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- TYHUGKGZNOULKD-UHFFFAOYSA-N 1-fluoro-2-iodobenzene Chemical compound FC1=CC=CC=C1I TYHUGKGZNOULKD-UHFFFAOYSA-N 0.000 claims description 7
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 claims description 7
- AJZFEJQZIOIQSR-UHFFFAOYSA-M potassium;diphenyl phosphate Chemical compound [K+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 AJZFEJQZIOIQSR-UHFFFAOYSA-M 0.000 claims description 7
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000005424 photoluminescence Methods 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000010521 absorption reaction Methods 0.000 abstract description 5
- 238000004020 luminiscence type Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 90
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000013078 crystal Substances 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 238000005406 washing Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000001816 cooling Methods 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 238000002390 rotary evaporation Methods 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- 229940045803 cuprous chloride Drugs 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000695 excitation spectrum Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 Ir (I) Chemical class 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- DKMKRQIXLINHFC-UHFFFAOYSA-N P.P.C=1C=CNC=1 Chemical compound P.P.C=1C=CNC=1 DKMKRQIXLINHFC-UHFFFAOYSA-N 0.000 description 1
- 238000004224 UV/Vis absorption spectrophotometry Methods 0.000 description 1
- 238000004847 absorption spectroscopy Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005415 bioluminescence Methods 0.000 description 1
- 230000029918 bioluminescence Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002503 iridium Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000000373 single-crystal X-ray diffraction data Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 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
- C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
- C07F9/6503—Five-membered rings
- C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
- C07F9/65068—Five-membered rings having the nitrogen atoms in positions 1 and 3 condensed with carbocyclic rings or carbocyclic ring systems
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- 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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
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- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention belongs to the technical field of synthesis of organic complexes, and relates to a luminescent copper compound based on a benzimidazole diphosphine ligand and a preparation method thereof. The molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuXN2P2The structural formula is shown as formula I. The luminescent copper compound has strong absorption (epsilon) near 230nm>5×104L·mol‑1·cm‑1) The medium-intensity absorption within the range of 280-300 nm has the luminous quantum efficiency of 71.53% at 293K, the service life of 61.08 mu s, and the material is a high-efficiency OLED photoluminescence material and can be used in the field of OLED luminescence material preparation.
Description
Technical Field
The invention belongs to the technical field of synthesis of organic complexes, and relates to a luminescent copper compound based on a benzimidazole diphosphine ligand and a preparation method thereof.
Background
With the continuous development of society and scientific technology, luminescent materials become one of the most active topics in the field of material research. Luminescent materials are of various types, and can be classified into photoluminescence, electroluminescence, bioluminescence, chemiluminescence, and the like, by the classification of the luminescent energy source. Electroluminescent devices are continually being investigated in various different light emission types. Organic electroluminescent devices (OLEDs) are becoming the mainstream trend of energy-saving lighting and novel display technologies due to their excellent characteristics of ultra-thinness, low power consumption, high contrast, natural color, flexible display, etc., and have been used in life, for example, the latest mobile display terminals nowadays are P40 series. Stable, efficient, inexpensive light emitting materials are the core of OLEDs.
The influential and pioneering search of s.r.forrest et al in 1998 found that organometallic complexes can achieve rapid intersystem crossing (ISC) and long-lived phosphorescence decay due to their strong spin-orbit coupling (S ℃). Research finds that phosphorescent complexes using transition metal atoms are receiving more and more attention because they can trap singlet and triplet excitons simultaneously, improve the luminous efficiency of the complexes, and thus theoretically achieve internal quantum efficiencies up to 100% in OLEDs. However, the d6 and d8 complexes of the transition metals such as Ir (I), Pt (II) and Os (III) are expensive, not abundant and have large pollution, which prevents the application of the transition metals in mass production. Therefore, it is highly desirable to develop inexpensive, earth-abundant transition metal complexes.
In OLED light-emitting material applications, cu (i) complexes are considered as an alternative to the commonly used phosphorescent iridium complexes. The cuprous complex has the advantages of rich resources, low cost, various coordination structures, excellent luminescence property and the like. Therefore, the cuprous has unique advantages in the aspect of developing new cheap high-performance luminescent materials, and further develops a cuprous complex as an OLED luminescent material, so that the cuprous complex has extremely important scientific research value and economic value.
Disclosure of Invention
In order to overcome the disadvantages and drawbacks of the prior art, the present invention has a primary object to provide a luminescent copper compound based on a benzimidazole bisphosphine ligand, which has a better photoluminescence property.
The invention also aims to provide a preparation method of the luminescent copper compound based on the benzimidazole diphosphine ligand, which has mild reaction conditions and simple preparation process.
Still another object of the present invention is to provide the use of the above luminescent copper compound based on a benzimidazolium bisphosphine ligand.
The purpose of the invention is realized by the following technical scheme:
a luminescent copper compound based on a benzimidazole diphosphine ligand has a molecular formula of C43H32CuXN2P2The structural formula is shown as formula I:
wherein X is I, Cl or Br, Ph is phenyl;
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuIN2P2When the structure unit belongs to an orthorhombic system, the molecular weight is 829.08, and the space group is P212121The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°；
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuClN2P2When the structural unit belongs to monoclinic system, the molecular weight is 737.63, and the space groupIs P21/c, the unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝113.44(3)°；
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuBrN2P2When the structure unit belongs to an orthorhombic system, the molecular weight is 814.35, and the space group is P212121The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°；
the preparation method of the luminescent copper compound based on the benzimidazole diphosphine ligand comprises the following steps:
(1) mixing o-nitroaniline, o-fluoroiodobenzene, a palladium catalyst, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine, alkali and a solvent, and reacting for 24-36 h at 115-120 ℃ under the inert gas atmosphere and oil bath conditions; after the reaction is finished, purifying the product to obtain an intermediate compound A;
(2) mixing the intermediate compound A prepared in the step (1), o-fluorobenzaldehyde, sodium hydrosulfite and a solvent, and stirring and reacting for 4-6 h at 130-135 ℃ under the condition of oil bath; purifying the product after the reaction is finished to obtain an intermediate compound B;
(3) mixing the intermediate compound B prepared in the step (2), potassium diphenylphosphate and a solvent, carrying out reflux reaction at 85 ℃ for 36-48 h in an inert gas atmosphere, and purifying a product after the reaction is finished to obtain a ligand L;
(4) dissolving the ligand L prepared in the step (3) in a solvent, adding cuprous halide, stirring for 2-3 h at 20-35 ℃, standing for 10-20 min, performing solid-liquid separation, and purifying the product to obtain a luminescent copper compound based on the benzimidazole diphosphine ligand;
the structural formulas of the intermediate compound A, the intermediate compound B and the ligand L are shown as a formula II, a formula III and a formula IV:
wherein Ph is phenyl;
the mol ratio of the o-nitroaniline, the o-fluoroiodobenzene and the binaphthyl-2, 2' -bis-diphenylphosphine in the step (1) is preferably 5:6: 0.37;
the palladium catalyst in step (1) is preferably bis (dibenzylideneacetone) palladium;
the molar ratio of the palladium catalyst to the o-nitroaniline in the step (1) is preferably 1: 20;
the base in step (1) is preferably cesium carbonate;
the molar ratio of the alkali to the o-nitroaniline in the step (1) is preferably 2: 1;
the solvent in the step (1) is preferably toluene;
the inert gas in the step (1) is preferably argon;
the condition of purification in the step (1) is preferably that after the reaction is finished, the solvent is removed by cooling and reduced pressure distillation, dichloromethane and water are respectively adopted for extraction, and the organic phase is subjected to rotary evaporation to obtain an intermediate compound A;
the molar ratio of the intermediate compound A, the o-fluorobenzaldehyde and the sodium hydrosulfite in the step (2) is preferably 10:12: 40;
the solvent in the step (2) is a mixture of methanol and water, wherein the volume ratio of the methanol to the water is preferably 5: 1;
the purification in step (2) is preferably:
cooling after the reaction is finished, carrying out rotary evaporation to recover the solvent, extracting with ethyl acetate and water respectively, and carrying out rotary evaporation on the organic phase to obtain an intermediate compound B;
the solvent in the step (3) is preferably tetrahydrofuran;
the molar ratio of the intermediate compound B to potassium diphenylphosphate described in step (3) is preferably 1: 3;
the inert gas in the step (3) is preferably argon;
the purification in step (3) is preferably:
cooling after the reaction is finished, adding methanol for soaking, taking and washing the solid after the solid is separated out, and drying in vacuum to obtain a ligand L;
the cuprous halide in the step (4) is cuprous iodide, cuprous chloride or cuprous bromide;
the molar ratio of the ligand L to the cuprous halide in the step (4) is preferably 1: 1;
the solvent in the step (4) is preferably a mixture of dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is preferably (3-5): 1;
the purification in step (4) is preferably:
after solid-liquid separation, volatilizing the obtained liquid at the temperature of 20-35 ℃ for 48-72 hours to obtain a crystal crude product of the luminescent copper compound based on the benzimidazole diphosphine ligand, washing the crystal crude product with methanol, and drying in vacuum to obtain the luminescent copper compound based on the benzimidazole diphosphine ligand;
the application of the luminescent copper compound based on the benzimidazole diphosphine ligand in the field of OLED luminescent materials;
compared with the prior art, the invention has the following advantages and effects:
(1) the luminescent copper compound based on the benzimidazole diphosphine ligand has strong absorption (epsilon) near 230nm in the ultraviolet-visible absorption spectrum>5×104L·mol-1·cm-1) Medium intensity absorption occurs in the range of 280-300 nm.
(1) The invention provides luminescent copper compounds (1), (2) and (3) (C) based on benzimidazole diphosphine ligand43H32CuIN2P2、C43H32CuClN2P2And C43H32CuBrN2P2) Having maximum emission wavelengths of 629nm, 652nm and 616nm, C43H32CuIN2P2And C43H32CuBrN2P2Exhibits orange-red light emission, and C43H32CuClN2P2Is red-shifted and appears as red emission.
(3) The invention provides a benzimidazole-based productLuminescent copper compounds (1), (2) and (3) (C) of Azole bisphosphine ligand43H32CuIN2P2、C43H32CuClN2P2And C43H32CuBrN2P2) The luminescence quantum efficiency of the solid powder at 293K reaches 59.91%, 15.73% and 71.53%, respectively, wherein C is43H32CuBrN2P2The life of (2) reaches 61.08 mu s.
(4) The light-emitting copper compound based on the benzimidazole diphosphine ligand is a high-efficiency OLED photoluminescence material and can be used in the field of OLED luminescence material preparation.
Drawings
FIG. 1 is a schematic diagram of the crystal structure of a luminescent copper compound (1).
Fig. 2 is a schematic diagram of the crystal structure of the luminescent copper compound (2).
Fig. 3 is a schematic diagram of the crystal structure of the luminescent copper compound (3).
FIG. 4 is a graph of the UV-VIS absorption spectra of three luminescent copper compounds.
FIG. 5 is a graph of excitation and emission spectra of three luminescent copper compounds at 293K, where ex denotes the excitation spectrum and em denotes the emission spectrum.
FIG. 6 is a graph of the emission spectra of three luminescent copper compounds at a low temperature of 77K.
FIG. 7 is a scheme for the synthesis of ligand L, wherein Ph represents a phenyl group.
FIG. 8 is a scheme for the synthesis of copper compounds, wherein Ph represents a phenyl group.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
(1) 10mL of toluene, o-nitroaniline (0.69g, 5mmol), o-fluoroiodobenzene (1.04mL, 6mmol), bis (dibenzylideneacetone) palladium (0.144g, 0.25mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.233g, 0.37mmol) and cesium carbonate (3.26g, 10mmol) were added to a 50mL three-necked flask, and the three-necked flask was placed in an oil bath and reacted at 120 ℃ for 24 hours under an argon atmosphere; after the reaction is finished, cooling to room temperature, carrying out reduced pressure distillation to remove toluene, extracting with 25ml of dichloromethane and 25ml of distilled water respectively, and carrying out rotary evaporation on an organic phase to obtain an intermediate compound A;
(2) adding 100mL of anhydrous methanol, 20mL of distilled water, the intermediate compound A (2.3006g, 10mmol) prepared in the step (1), o-fluorobenzaldehyde (1.488g, 12mmol) and sodium hydrosulfite (7g, 40mmol) into a 250mL three-neck flask, placing the three-neck flask into an oil bath kettle, reacting for 6 hours at 130 ℃ under magnetic stirring, cooling to room temperature, carrying out rotary evaporation to recover the solvent, extracting with 25mL of ethyl acetate and 20mL of distilled water respectively, and carrying out rotary evaporation on the organic phase to obtain an intermediate compound B;
(3) adding the intermediate compound B (1.53g, 5mmol) prepared in the step (2), potassium diphenylphosphate (3.36g, 15mmol) and 20mL of anhydrous tetrahydrofuran solvent into a 100mL three-neck flask, carrying out reflux reaction at 85 ℃ for 36h under the protection of argon, cooling to room temperature after the reaction is finished, adding 5mL of methanol solution for soaking, washing with 10mL of distilled water after solid is separated out, and carrying out vacuum drying to obtain a ligand L; FIG. 7 is a scheme for the synthesis of ligand L.
(4) Adding the ligand L (0.191g, 0.3mmol) prepared in the step (3) into a 50mL beaker, then respectively adding dichloromethane (25mL) and anhydrous methanol (5mL), after the ligand is completely dissolved, adding cuprous iodide (0.057g, 0.3mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 25mL small bottle, volatilizing at room temperature for 48h to obtain a crystal of a copper compound (1), washing the crystal with 3mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely a luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 47%; wherein, fig. 8 is a synthesis scheme of the copper compound.
(5) Adding the ligand L (0.191g, 0.3mmol) prepared in the step (3) into a 50mL beaker, then respectively adding dichloromethane (20mL) and anhydrous methanol (5mL), after the ligand is completely dissolved, adding cuprous chloride (0.0297g, 0.3mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 25mL small bottle, volatilizing at room temperature for 60h to obtain a crystal of a copper compound (2), washing the crystal with 3mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (2), namely a luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 52%;
(6) adding the ligand L (0.191g, 0.3mmol) prepared in the step (3) into a 50mL beaker, then respectively adding dichloromethane (15mL) and anhydrous methanol (5mL), after the ligand is completely dissolved, adding cuprous bromide (0.043g, 0.3mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 25mL small bottle, volatilizing at room temperature for 72h to obtain a crystal of the copper compound (3), washing the crystal with 3mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (3), namely the luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 42%.
Example 2
(1) In a 100mL three-neck flask were added 20mL of toluene, o-nitroaniline (1.38g, 10mmol), o-fluoroiodobenzene (2.08mL, 12mmol), bis (dibenzylideneacetone) palladium (0.288g, 0.5mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.466g, 0.74mmol), and cesium carbonate (6.52g, 20mmol), and the three-neck flask was placed in an oil bath and reacted at 115 ℃ for 36 hours under an argon atmosphere; after the reaction is finished, cooling to room temperature, carrying out reduced pressure distillation to remove toluene, extracting with 30ml of dichloromethane and 50ml of distilled water respectively, and carrying out rotary evaporation on an organic phase to obtain an intermediate compound A;
(2) adding 200mL of anhydrous methanol, 40mL of distilled water, the intermediate compound A (4.6g, 20mmol) prepared in the step (1), o-fluorobenzaldehyde (2.97g, 24mmol) and sodium hydrosulfite (14g, 80mmol) into a 500mL three-neck flask, placing the three-neck flask into an oil bath pot, reacting for 4 hours at 135 ℃ under magnetic stirring, cooling to room temperature, carrying out rotary evaporation to recover the solvent, extracting with 50mL of ethyl acetate and 40mL of distilled water respectively, and carrying out rotary evaporation on the organic phase to obtain an intermediate compound B;
(3) adding the intermediate compound B (3.06g, 10mmol) prepared in the step (2), potassium diphenylphosphate (6.72g, 30mmol) and 40mL of anhydrous tetrahydrofuran solvent into a 100mL three-neck flask, carrying out reflux reaction at 85 ℃ for 48h under the protection of argon, cooling to room temperature after the reaction is finished, adding 10mL of methanol solution for soaking, washing with 20mL of distilled water after solid is separated out, and carrying out vacuum drying to obtain a ligand L;
(4) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous iodide (0.114g, 0.6mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 50mL small bottle, volatilizing at room temperature for 72h to obtain a crystal of a copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely a luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 49%;
(5) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous chloride (0.06g, 0.6mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 50mL small bottle, volatilizing at room temperature for 72h to obtain a crystal of a copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely the luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 55%;
(6) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous bromide (0.086g, 0.6mmol), stirring at room temperature for 2h, standing for 10min, filtering, transferring the obtained solution into a 50mL small bottle, volatilizing at room temperature for 72h to obtain a crystal of the copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely the luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 45%.
Example 3
(1) In a 100mL three-necked flask, 20mL of toluene, o-nitroaniline (1.38g, 10mmol), o-fluoroiodobenzene (2.08mL, 12mmol), bis (dibenzylideneacetone) palladium (0.288g, 0.5mmol), 1 '-binaphthyl-2, 2' -bisdiphenylphosphine (0.466g, 0.74mmol) and cesium carbonate (6.52g, 20mmol) were added, and the three-necked flask was placed in an oil bath and reacted at 118 ℃ for 30 hours under an argon atmosphere; after the reaction is finished, cooling to room temperature, carrying out reduced pressure distillation to remove toluene, extracting with 30ml of dichloromethane and 50ml of distilled water respectively, and carrying out rotary evaporation on an organic phase to obtain an intermediate compound A;
(2) adding 200mL of anhydrous methanol, 40mL of distilled water, the intermediate compound A (4.6g, 20mmol) prepared in the step (1), o-fluorobenzaldehyde (2.97g, 24mmol) and sodium hydrosulfite (14g, 80mmol) into a 500mL three-neck flask, placing the three-neck flask into an oil bath pot, reacting for 5 hours at 132 ℃ under magnetic stirring, cooling to room temperature, carrying out rotary evaporation to recover the solvent, extracting with 50mL of ethyl acetate and 40mL of distilled water respectively, and carrying out rotary evaporation on the organic phase to obtain an intermediate compound B;
(3) adding the intermediate compound B (3.06g, 10mmol) prepared in the step (2), potassium diphenylphosphate (6.72g, 30mmol) and 40mL of anhydrous tetrahydrofuran solvent into a 100mL three-neck flask, carrying out reflux reaction at 85 ℃ for 40h under the protection of argon, cooling to room temperature after the reaction is finished, adding 10mL of methanol solution for soaking, washing with 20mL of distilled water after solid is separated out, and carrying out vacuum drying to obtain a ligand L;
(4) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous iodide (0.114g, 0.6mmol), stirring at room temperature for 2.5h, standing for 15min, filtering, transferring the obtained solution into a 50mL vial, volatilizing at room temperature for 72h to obtain a crystal of a copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely a luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 48%;
(5) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous chloride (0.06g, 0.6mmol), stirring at room temperature for 2.5h, standing for 15min, filtering, transferring the obtained solution into a 50mL vial, volatilizing at room temperature for 72h to obtain a crystal of a copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely a luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 56%;
(6) adding the ligand L (0.382g, 0.6mmol) prepared in the step (3) into a 100mL beaker, then respectively adding dichloromethane (30mL) and anhydrous methanol (10mL), after the ligand is completely dissolved, adding cuprous bromide (0.086g, 0.6mmol), stirring at room temperature for 2.5h, standing for 15min, filtering, transferring the obtained solution into a 50mL small bottle, volatilizing at room temperature for 72h to obtain a crystal of a copper compound (1), washing the crystal with 10mL of anhydrous methanol, and drying in vacuum to obtain a pure product of the copper compound (1), namely the luminescent copper compound based on the benzimidazole diphosphine ligand, wherein the yield is 43%.
Effects of the embodiment
Luminescent copper compounds (1), (2) and (3) (C) based on a benzimidazoledipine ligand prepared in examples 1, 2 and 343H32CuIN2P2、C43H32CuClN2P2And C43H32CuBrN2P2) And (3) carrying out characterization detection:
(1) crystal structure
Under microscope, three kinds of single crystal samples of copper compound with proper size and smooth surface are selected, and monochromic reaction is carried out by graphite at proper temperature by using Bruker AMART APEX II CCD X-ray single crystal diffractometer
Single crystal X-ray diffraction data were collected and absorption corrected using the multiple scanning procedure (SADABS). All structures were solved by a direct method and by F-based using the SHELXTL package and the Olex2 program2The full matrix least square method of (2) is refined. Hydrogen atoms are added at ideal positions and an anisotropic refinement is used for all non-hydrogen atoms. The crystal structures of the three copper compounds are schematically shown in fig. 1, fig. 2 and fig. 3. Some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in the following table:
TABLE 1 partial parameters for crystallographic diffraction point data collection and structure refinement
(2) Ultraviolet-visible absorption spectroscopy
UV-VIS absorption Spectroscopy Using a Perkin-Elmer Lambda 365 UV spectrometer, ligand L and three luminescent copper compounds (1), (2) and (3) (C) were combined at room temperature43H32CuIN2P2、C43H32CuClN2P2And C43H32CuBrN2P2) Respectively dissolved in dichloromethane to give a concentration of 1.0 × 10-5The ultraviolet-visible absorption spectrum of the solution in mol/L is shown in FIG. 4.
(3) Analysis of photoluminescence Properties
Emission spectrum analysis was carried out by using an F-4600 type fluorescence spectrometer, as shown in FIG. 5, in which ex represents an excitation spectrum, em represents an emission spectrum, and the maximum emission wavelengths of the copper compound (1), the copper compound (2) and the copper compound (3) under the condition of 293K were 629nm, 616nm and 652nm, respectively; the luminescence life is measured by an FLS980 type steady-state transient fluorescence spectrometer, and the life of the copper compound (3) of the solid powder under the condition of 293K reaches 61.08 mu s; the absolute quantum yield is measured by an FLS980 type steady-state transient fluorescence spectrometer with an integrating sphere, and the photoluminescence quantum efficiency of the solid powder under the condition of 293K reaches 59.91%, 15.73% and 71.53% respectively. FIG. 6 is a graph of the emission spectra of three luminescent copper compounds at a low temperature of 77K.
(4) Nuclear magnetic characterization
Nuclear magnetic analyses of the intermediate compound A, B, the ligand L, the copper compound (1), the copper compound (2), and the copper compound (3) obtained in examples 1, 2, and 3 were carried out using a Br ker DPX-400MGHz superconducting nuclear magnetic resonance apparatus.
Intermediate compound a:1H NMR(300MHz,CDCl3)δ9.31(s,1H),8.24(dd,J＝8.7,1.5Hz,1H),7.44–7.37(m,2H),7.24–7.18(m,3H),7.08(dt,J＝2.9,1.5,1.4Hz,1H),6.83(m,J＝7.2,7.0,1.2Hz,1H).13C NMR(151MHz,DMSO)δ157.77,156.14,142.26,136.62,133.85,127.75(d,J＝7.7Hz),127.16(d,J＝11.7Hz),126.58,125.69(d,J＝3.4Hz),118.66,116.99,116.88(d,J＝4.0Hz).
intermediate compound B:1H NMR(400MHz,CDCl3)δ7.95(d,J＝7.8Hz,1H),7.72(td,J＝7.5,1.7Hz,1H),7.49–7.27(m,6H),7.22(dd,J＝7.9,4.5Hz,3H),7.00(t,J＝9.0Hz,1H).13C NMR(151MHz,CDCl3)δ160.72,159.05,158.10,156.43,148.96,143.59,142.04,136.29,132.17,132.04(d,J＝7.9Hz),130.58(d,J＝7.6Hz),129.19,124.75(d,J＝4.0Hz),124.38,123.91,123.20(d,J＝4.9Hz),120.13,116.96(d,J＝19.3Hz),115.88(d,J＝21.3Hz),110.52.
ligand L:1H NMR(600MHz,CDCl3)δ7.73(d,J＝8.0Hz,1H),7.54–7.47(m,2H),7.33–7.26(m,6H),7.22(dd,J＝11.8,6.6Hz,9H),7.20–7.12(m,7H),7.08(q,J＝7.1Hz,3H),6.98–6.89(m,3H),6.58(d,J＝8.0Hz,1H).13C NMR(151MHz,CDCl3)δ152.75,142.51,141.00(d,J＝27.4Hz),139.05,138.92,138.14,137.32,137.15,136.94,136.64,136.56,136.02,135.93,135.48,134.76,134.22,134.07,133.67,133.54,133.41,133.29,133.01,132.89,131.67(d,J＝6.6Hz),130.22,130.15,129.26,128.96,128.38(d,J＝5.2Hz),128.32,128.22(d,J＝5.4Hz),128.12,127.99,122.74,122.01,119.84,110.63.31P NMR(243MHz,CDCl3)δ-12.53(s),-19.15(s).
copper compound (1):1H NMR(600MHz,CDCl3)δ7.98–7.90(m,1H),7.77–7.69(m,1H),7.63(dd,J＝18.5,7.8Hz,1H),7.56(t,J＝7.0Hz,1H),7.47(dd,J＝17.7,9.8Hz,3H),7.42(dd,J＝8.4,3.7Hz,1H),7.38–7.28(m,3H),7.24(d,J＝7.4Hz,1H),7.18(tt,J＝8.6,5.2Hz,2H),7.03(dd,J＝12.4,7.0Hz,2H),6.82(t,J＝8.7Hz,1H),6.65–6.57(m,1H),6.49(t,J＝9.6Hz,1H).
copper compound (2):1H NMR(600MHz,CDCl3)δ7.97–7.85(m,2H),7.73–7.67(m,1H),7.63(dd,J＝15.7,7.8Hz,2H),7.59–7.44(m,8H),7.43–7.39(m,1H),7.33(dd,J＝18.0,7.9Hz,4H),7.27(d,J＝6.7Hz,2H),7.23–7.17(m,4H),7.04(t,J＝7.2Hz,2H),6.93(t,J＝7.6Hz,1H),6.82(t,J＝8.7Hz,2H),6.77–6.67(m,2H),6.39(d,J＝8.0Hz,1H).
copper compound (3):1H NMR(600MHz,CDCl3)δ7.97–7.85(m,1H),7.73–7.67(m,1H),7.63(dd,J＝15.7,7.8Hz,1H),7.59–7.44(m,4H),7.43–7.39(m,1H),7.33(dd,J＝18.0,7.9Hz,2H),7.27(d,J＝6.7Hz,1H),7.23–7.17(m,2H),7.04(t,J＝7.2Hz,1H),6.93(t,J＝7.6Hz,1H),6.82(t,J＝8.7Hz,1H),6.77–6.67(m,1H),6.39(d,J＝8.0Hz,1H).
the above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A luminescent copper compound based on a benzimidazole diphosphine ligand is characterized in that the molecular formula is C43H32CuXN2P2The structural formula is shown as formula I:
wherein X is I, Cl or Br, Ph is phenyl.
2. A luminescent copper compound based on a benzimidazole bisphosphine ligand according to claim 1, characterized in that:
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuIN2P2When the structure unit belongs to an orthorhombic system, the molecular weight is 829.08, and the space group is P212121The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°；
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuClN2P2When the structure unit belongs to monoclinic system, the molecular weight is 737.63, the space group is P21/c, and the unit cell parameters are as follows:
α＝90.00(3)°，γ＝90.00(3)°，β＝113.44(3)°；
the molecular formula of the luminescent copper compound based on the benzimidazole diphosphine ligand is C43H32CuBrN2P2When the structure unit belongs to an orthorhombic system, the molecular weight is 814.35, and the space group is P212121The unit cell parameters are:
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°。
3. the method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 1 or 2, characterized by comprising the steps of:
(1) mixing o-nitroaniline, o-fluoroiodobenzene, a palladium catalyst, 1 '-binaphthyl-2, 2' -bis-diphenylphosphine, alkali and a solvent, and reacting for 24-36 h at 115-120 ℃ under the inert gas atmosphere and oil bath conditions; after the reaction is finished, purifying the product to obtain an intermediate compound A;
(2) mixing the intermediate compound A prepared in the step (1), o-fluorobenzaldehyde, sodium hydrosulfite and a solvent, and stirring and reacting for 4-6 h at 130-135 ℃ under the condition of oil bath; purifying the product after the reaction is finished to obtain an intermediate compound B;
(3) mixing the intermediate compound B prepared in the step (2), potassium diphenylphosphate and a solvent, carrying out reflux reaction at 85 ℃ for 36-48 h in an inert gas atmosphere, and purifying a product after the reaction is finished to obtain a ligand L;
(4) and (3) dissolving the ligand L prepared in the step (3) in a solvent, adding cuprous halide, stirring for 2-3 h at 20-35 ℃, standing for 10-20 min, performing solid-liquid separation, and purifying the product to obtain the luminescent copper compound based on the benzimidazole diphosphine ligand.
4. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
the structural formulas of the intermediate compound A, the intermediate compound B and the ligand L are shown as a formula II, a formula III and a formula IV:
wherein Ph is phenyl.
5. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
the molar ratio of the o-nitroaniline, the o-fluoroiodobenzene and the binaphthyl-2, 2' -bis-diphenylphosphine in the step (1) is 5:6: 0.37.
6. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
the molar ratio of the palladium catalyst to the o-nitroaniline in the step (1) is 1: 20;
the molar ratio of the alkali to the o-nitroaniline in the step (1) is 2: 1.
7. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
the molar ratio of the intermediate compound A, the o-fluorobenzaldehyde and the sodium hydrosulfite in the step (2) is 10:12: 40.
8. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
the molar ratio of the intermediate compound B to potassium diphenylphosphate described in step (3) is 1: 3.
9. The method for preparing a luminescent copper compound based on a benzimidazol bisphosphine ligand according to claim 3, wherein:
and (4) the molar ratio of the ligand L to the cuprous halide is 1: 1.
10. Use of a luminescent copper compound based on a benzimidazolium bisphosphine ligand according to claim 1 or 2 in the field of OLED luminescent materials.
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