CN114591365B - Luminous copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof - Google Patents
Luminous copper compound based on benzimidazole phosphine oxide ligand and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a benzimidazole phosphine oxide ligand-based luminescent copper compound, a preparation method and application thereof, wherein the molecular formula of the luminescent copper compound is C 64 H 49 CuRN 2 O 2 P 3 Each compound molecule contains one cuprous ion and one benzimidazole phosphine oxide ligand, wherein R in the benzimidazole phosphine oxide ligand represents H or Cl or CF 3 Represents a luminescent copper compound (1) or a luminescent copper compound (2) or a luminescent copper compound (3), respectively, which have different steric structures and luminescent properties. The maximum emission wavelengths of the luminescent copper compounds (1), (2) and (3) under the 293K condition are 475nm, 469nm and 464nm respectively; the solid powder has luminous quantum efficiencies of 46%, 58% and 76% at 293K, and lifetimes of 17.6us, 28.9us and 42.7us respectively. The preparation method has mild conditions and simple preparation process. The prepared luminescent copper compound is a high-efficiency photoluminescent material and can be used for preparing OLED luminescent devices.
Description
Technical Field
The invention belongs to the technical field of organic complex synthesis, and particularly relates to a benzimidazole phosphine oxide ligand-based luminescent copper compound, and a preparation method and application thereof.
Background
With the development of society, the scientific technology is continuously advanced, and various luminescent materials with excellent structure and good performance are invented successively. Substances that are capable of absorbing energy in some way to convert it into optical radiation are called luminescent materials and can be classified into photoluminescence, electroluminescence, and radiative luminescence, etc. in terms of luminescence. The organic electroluminescent material (OLED) is widely used in the fields of production and life due to the advantages of low power consumption, high efficiency, light weight, high contrast, rich luminescent colors, etc., such as the first global transparent television produced in volume and the notebook computer on the market in 2021, which are put forward by a company in 2020, all use OLED display technology.
Since the initial work made by Tang and vanselike in the 80 s of the 20 th century, organic materials have been widely used in OLED devices, and the metal organic complex phosphorescence electroluminescence phenomenon was reported by Forrest et al in 1998. Researches show that transition metals Ir (I), pt (II), os (III) and the like have strong spin coupling effect (SOC), 25% of excitons in a singlet state and 75% of excitons in a triplet state can be efficiently utilized, the limitation that the fluorescent material can only utilize 25% of excitons in the singlet state so that the quantum efficiency of the fluorescent material is low is broken through, and the light emitting performance of the fluorescent material is greatly improved. However, the commercial application of the noble metals such as Ir (I), pt (II) and Os (III) is restricted due to the factors such as high exploitation cost, high price, serious environmental pollution and the like. Therefore, there is a need to develop a resource-rich, inexpensive, and environmentally friendly luminescent material of metal complexes.
Among the various OLED luminescent materials, the monovalent copper complex is considered as a good substitute for noble metals, and has the advantages of abundant resources, low cost, little pollution and the like. And monovalent copper complexGood stability, various coordination modes and convenient regulation and control of luminescent color. Therefore, the research on monovalent copper complexes is of great importance in the development of novel, inexpensive and high-performance luminescent materials. In particular hybrid [ Cu (P≡P) (N≡N) ]] + Monovalent copper-like complexes (P+P and N+N are chelating biphosphorus and diimine ligands, respectively) are considered promising luminescent materials.
Disclosure of Invention
The invention aims to provide a light-emitting copper compound based on a benzimidazole phosphine oxide ligand, a preparation method and application thereof, and the prepared light-emitting copper compound based on the benzimidazole phosphine oxide ligand is a neutral light-emitting copper compound, has very good photoluminescence performance, can have different molecular formulas and structural formulas according to different substituents, has different light-emitting performance, and can be used for preparing OLED light-emitting devices.
One of the purposes of the present invention is to provide a luminescent copper compound based on benzimidazole phosphine oxide ligands, of the formula C 64 H 49 CuRN 2 O 2 P 3 The structural formula is shown as formula I:
wherein R is H or Cl or CF 3 Represents a luminescent copper compound (1) or a luminescent copper compound (2) or a luminescent copper compound (3), respectively, and Ph is phenyl.
Specifically:
when R is H, the luminous copper compound (1) has a molecular formula of C 64 H 50 CuN 2 O 2 P 3 The molecular weight is 1035.52, the structural unit belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows: α＝109.136(3)°，β＝91.377(3)°，γ＝112.098(4)°；
when R is Cl, the luminous copper compound (2) has a molecular formula of C 64 H 49 ClCuN 2 O 2 P 3 Molecular weight is 1069.95, structural unit belongs to monoclinic system, space group is P2 1 And/c, the unit cell parameters are as follows: α＝90°，β＝106.996(2)°，γ＝90°；
when R is CF 3 When the luminous copper compound (3) has a molecular formula of C 65 H 49 CuF 3 N 2 O 2 P 3 Molecular weight is 1103.51, structural unit belongs to monoclinic system, space group is P2 1 And/c, the unit cell parameters are as follows: α＝90°，β＝106.7110(10)°，γ＝90°。
the maximum emission wavelengths of the luminescent copper compound (1), the luminescent copper compound (2) and the luminescent copper compound (3) under the condition of 293K are 475nm, 469nm and 464nm respectively; the solid powder has luminous quantum efficiencies of 46%, 58% and 76% at 293K, and lifetimes of 17.6us, 28.9us and 42.7us respectively.
The invention also aims to provide a preparation method of the luminescent copper compound based on the benzimidazole phosphine oxide ligand, which specifically comprises the following steps:
(1) Sequentially adding the o-nitroaniline derivative and 2-diphenylphosphinobenzaldehyde into a mixed solution of absolute ethyl alcohol and water, and stirring to completely dissolve the o-nitroaniline derivative and the 2-diphenylphosphinobenzaldehyde; heating, adding sodium dithionite when the temperature reaches 35 ℃, refluxing and stirring for 5 hours at 75 ℃ under the conditions of inert gas atmosphere and oil bath, and purifying the product after the reaction is completed to obtain a ligand L;
(2) Dissolving the ligand L prepared in the step (1) and potassium hydroxide in a solvent I to obtain a mixed system I, dissolving copper tetrafluoroborate and 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene in a solvent II, stirring for 0.5h under an inert gas atmosphere to obtain a mixed system II, adding the mixed system II into the mixed system I, stirring for 1h, carrying out solid-liquid separation, and purifying the collected liquid to obtain a benzimidazole phosphine oxide ligand-based luminescent copper compound; wherein the solvent I is a mixed solution of dichloromethane and methanol in a volume ratio of 3:1; solvent II is methylene dichloride.
Wherein, the structural formula of the ligand L is shown as a formula II:
r is H or Cl or CF 3 Respectively represent hair ligands L 1 Or ligand L 2 Or ligand L 3 。
Further:
the molar ratio of the o-nitroaniline derivative, the 2-diphenylphosphinobenzaldehyde and the sodium dithionite in the step (1) is 1:1.2:4;
in the step (2), the molar ratio of the ligand L, potassium hydroxide, copper tetrafluoroborate tetraacetonitrile and 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene is 1:2:1:1.
Further:
the purification in the step (1) refers to: and after the reaction is finished, naturally cooling the product to room temperature, carrying out solid-liquid separation to remove solids, carrying out reduced pressure rotary evaporation to remove a solvent, completely extracting the obtained product by using ethyl acetate, mixing organic phases, adding anhydrous sodium sulfate to dry overnight, and finally carrying out column chromatography separation and purification by using an ethyl acetate/dichloromethane mixed solvent with the volume ratio of 1:10 as an eluent.
The purification in the step (2) refers to: volatilizing the collected liquid at room temperature to obtain a crystal crude product of the luminescent copper compound based on the benzimidazole phosphine oxide ligand, washing the crystal crude product with a small amount of methanol, and drying in vacuum.
Further:
o-nitro compound used in step (1)When the phenylamine derivative is o-nitroaniline, ligand L is obtained 1 Step (2) obtaining a luminescent copper compound (1);
when the o-nitroaniline derivative used in the step (1) is 4-chloro-2-nitroaniline, a ligand L is obtained 2 Step (2) to obtain a luminescent copper compound (2);
when the o-nitroaniline derivative used in the step (1) is 4-trifluoromethyl-2-nitroaniline, a ligand L is obtained 3 And (3) obtaining the luminescent copper compound (3) in the step (2).
It is a further object of the present invention to provide the use of the above-mentioned benzimidazole phosphine oxide ligand based luminescent copper compound in the field of OLED luminescent materials, which is a neutral luminescent copper compound with very good photoluminescence properties.
The invention has the following beneficial effects:
(1) The luminescent copper compound based on benzimidazole phosphine oxide ligand provided by the invention has strong absorption (epsilon) near 230nm in ultraviolet-visible absorption spectrum>5×10 4 L·mol -1 ·cm -1 ) The medium-intensity absorption occurs in the range of 270-320 nm;
(2) The invention provides a luminous copper compound based on benzimidazole phosphine oxide ligand, each molecule of the compound contains one cuprous ion and one benzimidazole phosphine oxide ligand, and the structural formula of the benzimidazole phosphine oxide ligand is shown as a formula II. R in the benzimidazole phosphine oxide ligand represents different groups, and different ligands are formed according to the difference of R, so that luminescent copper compounds with different chemical formulas and structural formulas are formed, and the luminescent copper compounds have different space structures and luminescent properties. Luminescent copper Compound (1) (C 64 H 50 CuN 2 O 2 P 3 ) Luminescent copper Compound (2) (C 64 H 49 ClCuN 2 O 2 P 3 ) And a luminescent copper compound (3) (C 65 H 49 CuF 3 N 2 O 2 P 3 ) Maximum emission wavelengths under 293K conditions were 475nm, 469nm and 464nm, respectively; the luminous quantum efficiency of the solid powder at 293K reaches 46%, 58% and 76%,the lifetimes were 17.6us, 28.9us and 42.7us, respectively;
(3) The preparation method of the light-emitting copper compound based on the benzimidazole phosphine oxide ligand provided by the invention has the advantages of mild condition, simple preparation process and simple operation. The prepared luminescent copper compound based on the benzimidazole phosphine oxide ligand is a high-efficiency photoluminescent material and can be used for preparing OLED luminescent devices.
Drawings
FIG. 1 is a schematic view of the crystal structure of a luminescent copper compound (1).
Fig. 2 is a schematic view of the crystal structure of the luminescent copper compound (2).
FIG. 3 is a schematic view of the crystal structure of the luminescent copper compound (3).
FIG. 4 is a graph of the ultraviolet-visible 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 represents the excitation spectrum and em represents the emission spectrum.
FIG. 6 is a synthetic scheme for ligand L, wherein Ph represents phenyl.
Fig. 7 is a synthetic route diagram of a copper compound, wherein Ph represents phenyl.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings. The following examples are based on the technology of the present invention and give detailed embodiments and operation steps, but the scope of the present invention is not limited to the following examples.
Example 1
(1) O-nitroaniline (1.38 g,10 mmol) and 2-diphenylphosphinobenzaldehyde (3.38 g,12 mmol) were weighed into a 150ml three-necked flask, and 100ml of absolute ethanol and 20ml of distilled water were sequentially added thereto, followed by stirring to dissolve them completely. Heating, adding sodium hydrosulfite (6.96 g,40 mmol) when the temperature reaches 35 ℃, refluxing and stirring for 5h at 75 ℃ under argon atmosphere and oil bath conditions, naturally cooling to room temperature after the reaction is finished, removing solids by suction filtration, and removing the solvent by rotary evaporation under reduced pressure. The resulting mixture was extracted completely with ethyl acetate, the organic phases were combined and dried overnight with anhydrous sodium sulfate. And finally, using an ethyl acetate/dichloromethane mixed solvent (the volume ratio of ethyl acetate to dichloromethane is 1:10) as an eluent to carry out column chromatography separation and purification to obtain the ligand L1, wherein the yield is 44%.
(2) Ligand L1 (0.1135 g,0.3 mmol) prepared in step (1) and KOH (0.0337 g,0.6 mmol) were added to a 50ml round bottom flask, and then dichloromethane (15 ml) and methanol (5 ml) were added and dissolved with stirring to give a mixed system I. Copper tetrafluoroborate (0.0943 g,0.3 mmol) and 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (0.1574 g,0.3 mmol) were dissolved in 10ml dichloromethane, and stirred under argon atmosphere for 0.5h to obtain a mixed system II, and the mixed system II was added to the above-mentioned mixed system I and stirred for 1h. Filtering, collecting the obtained liquid into a 10ml small bottle, volatilizing at room temperature to obtain a crystal crude product of the luminescent copper compound based on the benzimidazole phosphine oxide ligand, washing the crystal crude product with a small amount of methanol (3 ml), and vacuum drying to obtain the luminescent copper compound (1) based on the benzimidazole phosphine oxide ligand L1, wherein the yield is 40%.
Example 2
(1) 4-chloro-2-nitroaniline (1.72 g,10 mmol) and 2-diphenylphosphinobenzaldehyde (3.38 g,12 mmol) were weighed into a 150ml three-necked flask, and 100ml of absolute ethanol and 20ml of distilled water were sequentially added thereto, followed by stirring to dissolve them completely. Heating, adding sodium hydrosulfite (6.96 g,40 mmol) when the temperature reaches 35 ℃, refluxing and stirring for 5h at 75 ℃ under argon atmosphere and oil bath conditions, naturally cooling to room temperature after the reaction is finished, removing solids by suction filtration, and removing the solvent by rotary evaporation under reduced pressure. The mixture was extracted completely with ethyl acetate, the organic phases were combined and dried overnight with anhydrous sodium sulfate. Finally, using ethyl acetate/dichloromethane mixed solvent (the volume ratio of ethyl acetate to dichloromethane is 1:10) as eluent to carry out column chromatography separation and purification to obtain ligand L2, wherein the yield is 47%;
(2) Ligand L2 (0.1238 g,0.3 mmol) and KOH (0.0337 g,0.6 mmol) prepared in step (1) were added to a 50ml round-bottom flask, and then methylene chloride (15 ml) and methanol (5 ml) were added thereto and dissolved with stirring to give a mixed system I. Copper tetrafluoroborate (0.0943 g,0.3 mmol) and 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (0.1574 g,0.3 mmol) were dissolved in 10ml dichloromethane and stirred under argon atmosphere for 0.5h to obtain a mixed system II, and the mixed system II was added to the above-mentioned mixed system I and stirred for 1h. Filtering, collecting the obtained liquid into a 10ml small bottle, volatilizing at room temperature to obtain a crystal crude product of the luminescent copper compound based on the benzimidazole phosphine oxide ligand, washing the crystal crude product with a small amount of methanol (3 ml), and vacuum drying to obtain the luminescent copper compound (2) based on the benzimidazole phosphine oxide ligand L2, wherein the yield is 47%.
Example 3
(1) 4-trifluoromethyl-2-nitroaniline (2.06 g,10 mmol) and 2-diphenylphosphinobenzaldehyde (3.38 g,12 mmol) were weighed into a 150ml three-necked flask, and 100ml of absolute ethanol and 20ml of distilled water were sequentially added thereto, followed by stirring to dissolve them completely. Heating, adding sodium hydrosulfite (6.96 g,40 mmol) when the temperature reaches 35 ℃, refluxing and stirring for 5h at 75 ℃ under argon atmosphere and oil bath conditions, naturally cooling to room temperature after the reaction is finished, removing solids by suction filtration, and removing the solvent by rotary evaporation under reduced pressure. The mixture was extracted completely with ethyl acetate, the organic phases were combined and dried overnight with anhydrous sodium sulfate. And finally, using an ethyl acetate/dichloromethane mixed solvent (the volume ratio of ethyl acetate to dichloromethane is 1:10) as an eluent to carry out column chromatography separation and purification to obtain the ligand L3, wherein the yield is 45%.
(2) Ligand L3 (0.1339 g,0.3 mmol) and KOH (0.0337 g,0.6 mmol) prepared in step (1) were added to a 50ml round bottom flask, and then dichloromethane (15 ml) and methanol (5 ml) were added and dissolved with stirring to give a mixed system I. Copper tetrafluoroborate (0.0943 g,0.3 mmol) and 4, 5-bis-diphenylphosphine-9, 9-dimethylxanthene (0.1574 g,0.3 mmol) were dissolved in 10ml dichloromethane and stirred under argon atmosphere for 0.5h to obtain a mixed system II, and the mixed system II was added to the above-mentioned mixed system I and stirred for 1h. Filtering, collecting the obtained liquid into a 10ml small bottle, volatilizing at room temperature to obtain a crystal crude product of the luminescent copper compound based on the benzimidazole phosphine oxide ligand, washing the crystal crude product with a small amount of methanol (3 ml), and vacuum drying to obtain the luminescent copper compound (3) based on the benzimidazole phosphine oxide ligand L3, wherein the yield is 50%.
Effect examples
Prepared for example 1 to example 3The resulting benzimidazole phosphine oxide ligand-based luminescent copper compound (1) (C 64 H 50 CuN 2 O 2 P 3 ) Luminescent copper Compound (2) (C 64 H 49 ClCuN 2 O 2 P 3 ) And a luminescent copper compound (3) (C 65 H 49 CuF 3 N 2 O 2 P 3 ) And (3) performing characterization detection:
(1) Crystal structure
Under a microscope, three copper compound single crystal samples with proper size and smooth surface are selected, and a Bruker AMART APEX II CCD X-ray single crystal diffractometer is used for monochromatizing Cu-K alpha by graphite at proper temperatureSingle crystal diffraction data were collected by X-ray and absorption correction was performed using a multiple scanning procedure (sadbs). All structures were solved by direct methods and passed through an F-based using the SHELXTL package and the ole 2 program 2 Is refined by the full matrix least square method. Hydrogen atoms were added at the ideal positions and anisotropic finishing was used for all non-hydrogen atoms. The crystal structures of the three copper compounds are schematically shown in fig. 1, 2 and 3. The parameters of the crystallographic diffraction point data collection and structure refinement are shown in the following table:
TABLE 1 Crystal diffraction Point data collection and Structure refinement partial parameters
(2) Ultraviolet-visible absorption spectroscopy
The UV-visible absorption spectrum analysis was performed using a UV-1800PC type UV-visible spectrophotometer. Ligand L under room temperature conditions 1 、L 2 、L 3 And three luminescent copper compounds (1), (2) and (3) (C) 64 H 50 CuN 2 O 2 P 3 、C 64 H 49 ClCuN 2 O 2 P 3 And C 65 H 49 CuF 3 N 2 O 2 P 3 ) Respectively dissolving in dichloromethane to obtain a concentration of 1.0X10 -5 The measurement of the mol/L solution is carried out, and the ultraviolet-visible absorption spectrum is shown in FIG. 4: three luminescent copper compounds (1), (2) and (3) (C 64 H 50 CuN 2 O 2 P 3 、C 64 H 49 ClCuN 2 O 2 P 3 And C 65 H 49 CuF 3 N 2 O 2 P 3 ) Has strong absorption (epsilon) around 230nm>5×10 4 L·mol -1 ·cm -1 ) The medium-intensity absorption occurs in the range of 270 to 320 nm.
(3) Photoluminescence performance analysis
The emission spectrum analysis was carried out by using a F-4600 type fluorescence spectrometer, as shown in FIG. 5, wherein ex represents an excitation spectrum, em represents an emission spectrum, and maximum emission wavelengths of the copper compound (1), the copper compound (2) and the copper compound (3) under the condition of 293K are 475nm, 469nm and 464nm, respectively; the absolute quantum yield is measured by using an FLS980 type fluorescence spectrometer, the luminescence quantum yield of the solid powder under the 293K condition reaches 46%, 58% and 76%, and the luminescence life is 17.6us, 28.9us and 42.7us respectively.
(4) Nuclear magnetism and elemental analysis characterization
The nuclear magnetic analysis of the ligand L1, ligand L2, ligand L3, copper compound (1), copper compound (2) and copper compound (3) obtained in example 1-example 3 was performed using a Bruker DPX-400MGHz superconducting nuclear magnetic resonance apparatus; elemental analysis was performed using a PE 2400-type elemental analyzer.
Ligand L1: 1 H NMR(400MHz,CDCl 3 )δ13.36(s,1H),8.60–8.57(m,1H),7.72(tt,J＝7.8,1.5Hz,1H),7.66(dd,J＝6.5,2.5Hz,1H),7.62–7.59(m 1H),7.57(d,J＝1.7Hz,1H),7.46–7.42(m,3H),7.40–7.38(m,2H),7.38–7.34(m,4H),7.19–7.14(m,3H),7.14–7.08(m,1H). 31 P NMR(162MHz,CDCl 3 )δ37.81(s).
ligand L2: 1 H NMR(400MHz,CDCl 3 )13.46(s,1H),δ8.54–8.49(m,1H),7.88(s,1H),7.85–7.76(m,2H),7.65–7.51(m,2H),7.40(dd,J＝9.5,4.6Hz,4H),7.37–7.31(m,6H),7.19–7.14(m,1H). 31 P NMR(162MHz,CDCl 3 )δ37.97(s).
ligand L3: 1 H NMR(400MHz,CDCl 3 )δ13.80(s,1H),8.62–8.56(m,1H),7.93(s,1H),7.79–7.69(m,2H),7.63–7.56(m,4H),7.48(dd,J＝7.5,1.4Hz,1H),7.45(d,J＝1.3Hz,1H),7.44-7.41(m,1H),7.40(d,J＝2.9Hz,2H),7.39–7.35(m,3H),7.16(dd,J＝14.9,7.3Hz,1H). 31 P NMR(162MHz,CDCl 3 )δ38.19(s)；
copper compound (1): 1 H NMR(400MHz,CDCl3)δ8.04(s,1H),7.77–7.32(m,13H),7.24–6.86(m,26H),6.68(dd,J＝14.5,8.1Hz,1H),6.56(m,2H),6.31(s,1H),1.78–1.60(m,6H). 31 P NMR(162MHz,CDCl3)δ37.02(s),-16.30(s).Anal.Calcd/％:C,74.23；H,4.87；N,2.71.Found:C,74.21；H,4.90；N,2.73.
copper compound (2): 1 H NMR(400MHz,CDCl3)δ7.97(s,1H),7.89–7.26(m,9H),7.25–6.85(m,29H),6.82–6.51(m,2H),6.33(s,2H),1.96–1.54(m,6H). 31 P NMR(162MHz,CDCl3)δ37.09(s),-16.38(s).Anal.Calcd/％:C,71.84；H,4.62；N,2.62.Found:C,71.81；H,4.64；N,2.63.
copper compound (3): 1 H NMR(400MHz,CDCl3)δ8.05–7.71(m,2H),7.59(dd,J＝12.3,7.1Hz,2H),7.51(d,J＝7.0Hz,2H),7.48–7.27(m,5H),7.25–6.76(m,28H),6.75–6.50(m,2H),6.49–6.24(m,2H),1.84–1.63(m,6H). 31 P NMR(162MHz,CDCl3)δ36.83(s),-16.05(s).Anal.Calcd/％:C,70.74；H,4.48；N,2.54.Found:C,70.72；H,4.50；N,2.57.
the foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention without departing from the scope of the technical solution of the present invention will still fall within the scope of the technical solution of the present invention.
Claims (1)
1. Luminescent copper compound based on benzimidazole phosphine oxide ligand and used for OLED (organic light emitting diode)The field of optical materials is characterized in that the molecular formula is C 64 H 49 CuRN 2 O 2 P 3 The structural formula is shown as formula I:
wherein R is H or Cl or CF 3 Represents a luminescent copper compound (1) or a luminescent copper compound (2) or a luminescent copper compound (3), respectively, and Ph is phenyl; the preparation method comprises the following steps:
(1) Sequentially adding the o-nitroaniline derivative and 2-diphenylphosphinobenzaldehyde into a mixed solution of absolute ethyl alcohol and water, and stirring to completely dissolve the o-nitroaniline derivative and the 2-diphenylphosphinobenzaldehyde; heating, adding sodium dithionite when the temperature reaches 35 ℃, refluxing and stirring for 5 hours at 75 ℃ under the condition of inert gas atmosphere and oil bath, naturally cooling the product to room temperature after the reaction is completed, removing solids through solid-liquid separation, removing the solvent through reduced pressure rotary evaporation, completely extracting the obtained product by using ethyl acetate, combining the organic phases, adding anhydrous sodium sulfate to dry overnight, and finally carrying out column chromatography separation and purification by using an ethyl acetate/dichloromethane mixed solvent with the volume ratio of 1:10 as an eluent to obtain a ligand L, wherein the structural formula of the ligand L is shown as a formula II:
r is H or Cl or CF 3 The method comprises the steps of carrying out a first treatment on the surface of the Wherein, the mol ratio of the o-nitroaniline derivative to the 2-diphenylphosphinobenzaldehyde to the sodium dithionite is 1:1.2:4;
(2) Dissolving the ligand L prepared in the step (1) and potassium hydroxide in a solvent I to obtain a mixed system I, dissolving tetra-acetonitrile copper tetrafluoroborate and 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene in a solvent II, stirring for 0.5h under an inert gas atmosphere to obtain a mixed system II, adding the mixed system II into the mixed system I, stirring for 1h, carrying out solid-liquid separation, volatilizing the collected liquid at room temperature to obtain a crystal crude product of a luminescent copper compound based on benzimidazole phosphine oxide ligand, washing the crystal crude product with a small amount of methanol, and carrying out vacuum drying to obtain the luminescent copper compound based on benzimidazole phosphine oxide ligand; wherein the solvent I is a mixed solution of dichloromethane and methanol in a volume ratio of 3:1; solvent II is methylene dichloride; ligand L, potassium hydroxide, copper tetrafluoroborate and 4, 5-bis-diphenylphosphine-9, 9-dimethyl xanthene with the molar ratio of 1:2:1:1;
the o-nitroaniline derivative in the step (1) is selected from o-nitroaniline, 4-chloro-2-nitroaniline or 4-trifluoromethyl-2-nitroaniline;
when o-nitroaniline is selected, R is H, and the luminous copper compound (1) is obtained, and the molecular formula of the luminous copper compound is C 64 H 50 CuN 2 O 2 P 3 The molecular weight is 1035.52, the structural unit belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows:α= 109.136 (3) °, β= 91.377 (3) °, γ= 112.098 (4) °; the maximum emission wavelength of the solid powder under the 293K condition is 475nm, the luminous quantum efficiency of the solid powder under the 293K condition is 46%, and the service life is 17.6us;
when 4-chloro-2-nitroaniline is selected, R is Cl, and the luminous copper compound (2) with the molecular formula of C is obtained 64 H 49 ClCuN 2 O 2 P 3 Molecular weight is 1069.95, structural unit belongs to monoclinic system, space group is P2 1 And/c, the unit cell parameters are as follows:α=90°, β= 106.996 (2) °, γ=90°; the maximum emission wavelength of the solid powder under the 293K condition is 469nm, the luminous quantum efficiency of the solid powder under the 293K condition is 58%, and the service life is 28.9us;
when 4-trifluoromethyl-2-nitroaniline is selected, R is CF 3 To obtain luminescent copper compound (3) with molecular formula of C 65 H 49 CuF 3 N 2 O 2 P 3 Molecular weight is 1103.51, structural unit belongs to monoclinic system, space group is P2 1 /cThe unit cell parameters are:α=90°, β= 106.7110 (10) °, γ=90°; the maximum emission wavelength under the 293K condition is 464nm, the luminous quantum efficiency of the solid powder under the 293K condition is 76%, and the service life is 42.7us.
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