CN112010904B - Benzimidazole diphosphine Cu (I) complex and preparation method thereof - Google Patents

Benzimidazole diphosphine Cu (I) complex and preparation method thereof Download PDF

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CN112010904B
CN112010904B CN202010911810.8A CN202010911810A CN112010904B CN 112010904 B CN112010904 B CN 112010904B CN 202010911810 A CN202010911810 A CN 202010911810A CN 112010904 B CN112010904 B CN 112010904B
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尹国杰
张斌
宋宜乐
杜晨霞
张少文
楚希杰
邵建伟
赵丽红
母小明
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Luoyang Institute of Science and Technology
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Abstract

The invention belongs to the technical field of organic complex synthesis, and particularly relates to a benzimidazole diphosphine Cu (I) complex and a preparation method thereof. The molecular formula of the benzimidazole diphosphine Cu (I) complex is C56H40N4P2Cu2I2The structural formula is shown as formula I. In the ultraviolet-visible absorption spectrum of the benzimidazole diphosphine Cu (I) complex provided by the invention, strong absorption (epsilon) is generated near 230nm>5×104L·mol‑1·cm‑1) Medium-intensity absorption occurs within the range of 300-320 nm, the maximum excitation wavelength is 376nm, the maximum emission wavelength is 609nm, and efficient orange luminescence is represented; the solid powder has the light-emitting quantum efficiency (PLQYs) of 45% at 293K and the light-emitting life of 2.26 mu s, and is an excellent OLED photoluminescence material.
Figure DDA0002663572020000011

Description

Benzimidazole diphosphine Cu (I) complex and preparation method thereof
Technical Field
The invention belongs to the technical field of organic complex synthesis, and particularly relates to a benzimidazole diphosphine Cu (I) complex 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 defects and shortcomings of the prior art, the invention mainly aims to provide a Cu (I) complex of benzimidazole diphosphine, which has better luminescence property.
The invention also aims to provide a preparation method of the benzimidazole diphosphine Cu (I) complex, which has mild reaction conditions and simple preparation process.
The invention further aims to provide application of the benzimidazole diphosphine Cu (I) complex.
The purpose of the invention is realized by the following technical scheme:
a benzimidazole diphosphine Cu (I) complex, the molecular formula of which is C56H40N4P2Cu2I2The structural formula is shown as formula I:
Figure BDA0002663572000000021
wherein Ph represents a phenyl group;
the structural unit of the benzimidazole diphosphine Cu (I) complex belongs to an orthorhombic system, the molecular weight is 1211.81, and the space group is Pna21The unit cell parameters are:
Figure BDA0002663572000000022
Figure BDA0002663572000000023
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°；
the benzimidazole diphosphine Cu (I) complex contains one dimer Cu in each complex molecule2(μ-I)2Unit, Cu due to narrow coordination space provided by ligand2(μ-I)2The cells are in a slightly deformed planar quadrilateral configuration, and the distance between Cu … and Cu is
Figure BDA0002663572000000024
Greater than the sum of the Van der Waals radii of two Cu atoms
Figure BDA0002663572000000025
The Cu … Cu in the complex has no obvious interaction; the coordination environment around the Cu atom is a deformed tetrahedral configuration, and the central ion Cu and the N atom and the P atom on the ligand L form two stable five-membered chelate rings;
the preparation method of the benzimidazole diphosphine Cu (I) complex comprises the following steps:
(1) adding aniline, 2, 6-difluoronitrobenzene and anhydrous potassium fluoride into a solvent, and reacting for 12-15 h at 95-100 ℃; purifying the product after the reaction is finished to obtain an intermediate product A;
(2) adding the intermediate product A prepared in the step (1), m-phthalaldehyde and sodium hydrosulfite into a mixed solvent, carrying out reflux reaction at 125-130 ℃ for 6-8 h, and purifying the product after the reaction is finished to obtain an intermediate product B;
(3) adding the intermediate product B prepared in the step (2) into a solvent, slowly adding potassium diphenylphosphate, carrying out reflux reaction at the temperature of 80-85 ℃ for 36-48 h, and purifying the 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 iodide, and stirring for 2-3 h at 20-35 ℃; purifying the product after the reaction is finished to obtain a benzimidazole diphosphine Cu (I) complex;
the structural formulas of the intermediate product A, the intermediate product B and the ligand L are shown as formulas II-IV;
Figure BDA0002663572000000031
wherein Ph represents a phenyl group;
the mol ratio of the aniline, the 2, 6-difluoronitrobenzene and the anhydrous potassium fluoride in the step (1) is preferably 1.2:1: 1;
the solvent in step (1) is preferably dimethyl sulfoxide (DMSO);
step (1) in said purification is preferably:
after the reaction is finished, cooling the system to room temperature, then adding water into the reaction system, stirring until a precipitate is separated out, filtering and washing the precipitate, and drying to obtain an intermediate product A;
the mol ratio of the intermediate compound A, the m-phthalaldehyde and the sodium hydrosulfite in the step (2) is preferably 2:1: 6;
the mixed solvent in the step (2) is a mixture of ethanol and water, wherein the volume ratio of the ethanol to the water is preferably 5: 1;
the purification in step (2) is preferably:
after the reaction is finished, cooling the system to room temperature, performing rotary evaporation to recover the solvent, then extracting with ethyl acetate, collecting the organic phase, and concentrating; finally, further purifying by column chromatography, and drying in vacuum to obtain an intermediate product B; the eluent of the column chromatography is petroleum ether/ethyl acetate 2:1(V: V);
the molar ratio of the intermediate compound B to potassium diphenylphosphate described in step (3) is preferably 1: 2;
the solvent in the step (3) is preferably tetrahydrofuran;
the purification in step (3) is preferably:
after the reaction is finished, cooling the system to room temperature, carrying out rotary evaporation to recover the solvent, then adding methanol for soaking, taking and washing the solid after the solid is separated out, and carrying out vacuum drying to obtain a ligand L;
the molar ratio of the ligand L to the cuprous iodide in the step (4) is preferably 1: 2;
the solvent in step (4) is preferably dichloromethane;
the purification in step (4) is preferably:
after the reaction is finished, carrying out solid-liquid separation, volatilizing the obtained liquid at the temperature of 20-35 ℃ for 72-96 h, filtering to obtain a crude crystal product, washing the crude crystal product with methanol, and drying in vacuum to obtain a Cu (I) benzimidazole diphosphine complex;
the benzimidazole diphosphine Cu (I) complex is applied to the field of OLED luminescent materials;
compared with the prior art, the invention has the following advantages and effects:
(1) in the ultraviolet-visible absorption spectrum of the benzimidazole diphosphine Cu (I) complex provided by the invention, strong absorption (epsilon) is generated near 230nm>5×104L·mol-1·cm-1) Medium intensity absorption in the range of 300-320 nm.
(2) The benzimidazole diphosphine Cu (I) complex provided by the invention has good photoluminescence property at room temperature, the maximum excitation wavelength of the complex is 376nm, the maximum emission wavelength of the complex is 609nm, and the complex shows high-efficiency orange luminescence.
(3) The solid powder of the benzimidazole diphosphine Cu (I) complex provided by the invention has the light-emitting quantum efficiency (PLQYs) of 45% at 293K and the light-emitting service life of 2.26 mu s.
(4) The benzimidazole diphosphine Cu (I) complex provided by the invention is an excellent 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 Cu (I) complex of benzimidazole diphosphine.
FIG. 2 is a diagram showing UV-VIS absorption spectra of a Cu (I) complex of benzimidazoledipine and a ligand L.
FIG. 3 is a graph of excitation and emission spectra of Cu (I) complexes of benzimidazoledipine at 293K, where ex denotes the excitation spectrum and em denotes the emission spectrum.
FIG. 4 is a scheme for the synthesis of ligand L, in which Ph represents a phenyl group.
FIG. 5 is a scheme showing the scheme for the synthesis of Cu (I) complexes of benzimidazoles bisphosphines, in which Ph denotes 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) Adding aniline (3.3mL, 36.2mmol), 2, 6-difluoronitrobenzene (3mL, 30mmol) and anhydrous potassium fluoride (1.8g, 30mmol) into 9mL of dimethyl sulfoxide, stirring to dissolve completely, and reacting at 95 ℃ for 15 h; after the reaction is finished, cooling the system to room temperature, then adding 30mL of distilled water into the reaction system, stirring until a large amount of red precipitate appears, filtering the precipitate, washing the precipitate for 3 times by using 30mL (10mL multiplied by 3 times) of distilled water, filtering out a solid, and drying the solid in a drying oven to obtain an intermediate product A;
(2) adding the intermediate product A (7g, 20mmol) prepared in the step (1) and m-phthalaldehyde (1.34g, 10mmol) into 120ml of mixed solvent (the volume ratio of ethanol to water is 5:1), stirring for dissolving, then adding sodium hydrosulfite (20g, 120mmol), and carrying out reflux reaction at 125 ℃ for 8 hours; after the reaction is finished, cooling the system to room temperature, recovering ethanol in the system through rotary evaporation, then extracting with ethyl acetate, collecting an organic phase, and concentrating; finally, purification by column chromatography (eluent petroleum ether/ethyl acetate 2:1(V: V)), drying in vacuo to afford intermediate compound B;
(3) adding the intermediate product B (10mmol) prepared in the step (2) into 20mL tetrahydrofuran, stirring to dissolve the intermediate product B, slowly adding twice amount of potassium diphenylphosphate (20mmol), and carrying out reflux reaction at 80 ℃ for 48 hours; and after the reaction is finished, cooling the system to room temperature, carrying out rotary evaporation to recover tetrahydrofuran in the system, then soaking with 25ml of methanol, after solid is separated out, filtering and recovering the methanol, washing the solid with 5ml of methanol and 5ml of water in sequence, and carrying out vacuum drying to obtain the ligand L, wherein the figure 4 is a synthesis route diagram of the ligand L.
(4) Adding the ligand L (3mmol) prepared in the step (3) into 20mL of dichloromethane solution, adding CuI (6mmol), and stirring at room temperature for 2 h; after the reaction is finished, filtering, transferring the obtained solution to a small bottle, naturally volatilizing at room temperature for 72h to obtain a crude crystal, washing the crude crystal with methanol, and drying in vacuum to obtain the target copper complex, namely the benzimidazole diphosphine Cu (I) complex with the yield of 80%, wherein fig. 5 is a synthesis route diagram of the benzimidazole diphosphine Cu (I) complex.
Example 2
(1) Adding aniline (3.3mL, 36.2mmol), 2, 6-difluoronitrobenzene (3mL, 30mmol) and anhydrous potassium fluoride (1.8g, 30mmol) into 9mL of dimethyl sulfoxide, stirring to dissolve completely, and reacting at 100 ℃ for 12 h; after the reaction is finished, cooling the system to room temperature, then adding 30mL of distilled water into the reaction system, stirring until a large amount of red precipitate appears, filtering the precipitate, washing the precipitate for 3 times by using 30mL (10mL multiplied by 3 times) of distilled water, filtering out a solid, and drying the solid in a drying oven to obtain an intermediate product A;
(2) adding the intermediate product A (7g, 20mmol) prepared in the step (1) and m-phthalaldehyde (1.34g, 10mmol) into 120ml of mixed solvent (the volume ratio of ethanol to water is 5:1), stirring for dissolving, then adding sodium hydrosulfite (20g, 120mmol), and carrying out reflux reaction at 130 ℃ for 6 hours; after the reaction is finished, cooling the system to room temperature, recovering ethanol in the system through rotary evaporation, then extracting by using ethyl acetate, collecting an organic phase, and concentrating; finally, purification by column chromatography (eluent petroleum ether/ethyl acetate 2:1(V: V)), drying in vacuo to afford intermediate compound B;
(3) adding the intermediate product B (10mmol) prepared in the step (2) into 20mL tetrahydrofuran, stirring to dissolve the intermediate product B, slowly adding twice amount of potassium diphenylphosphate (20mmol), and carrying out reflux reaction at 85 ℃ for 36 h; after the reaction is finished, cooling the system to room temperature, carrying out rotary evaporation to recover tetrahydrofuran in the system, then soaking with 25ml of methanol, after solid is separated out, filtering and recovering the methanol, washing the solid with 5ml of methanol and 5ml of water in sequence, and carrying out vacuum drying to obtain a ligand L;
(4) adding the ligand L (3mmol) prepared in the step (3) into 20mL of dichloromethane solution, adding CuI (6mmol), and stirring at room temperature for 2 h; and after the reaction is finished, filtering, transferring the obtained solution to a small bottle, naturally volatilizing at room temperature for 96 hours to obtain a crude crystal, washing the crude crystal with methanol, and drying in vacuum to obtain the target copper complex, namely the benzimidazole diphosphine Cu (I) complex, with the yield of 85%.
Example 3
(1) Adding aniline (3.3mL, 36.2mmol), 2, 6-difluoronitrobenzene (3mL, 30mmol) and anhydrous potassium fluoride (1.8g, 30mmol) into 9mL of dimethyl sulfoxide, stirring to dissolve completely, and reacting at 98 ℃ for 14 h; after the reaction is finished, cooling the system to room temperature, then adding 30mL of distilled water into the reaction system, stirring until a large amount of red precipitate appears, filtering the precipitate, washing the precipitate for 3 times by using 30mL (10mL multiplied by 3 times) of distilled water, filtering out a solid, and drying the solid in a drying oven to obtain an intermediate product A;
(2) adding the intermediate product A (7g, 20mmol) prepared in the step (1) and m-phthalaldehyde (1.34g, 10mmol) into 120ml of mixed solvent (the volume ratio of ethanol to water is 5:1), stirring for dissolving, then adding sodium hydrosulfite (20g, 120mmol), and carrying out reflux reaction at 128 ℃ for 7 h; after the reaction is completed, cooling the system to room temperature, recovering ethanol in the system by rotary evaporation, then extracting with ethyl acetate, collecting the organic phase, concentrating, finally purifying by column chromatography (eluent is petroleum ether/ethyl acetate ═ 2:1(V: V)), and drying in vacuum to obtain an intermediate compound B;
(3) adding the intermediate product B (10mmol) prepared in the step (2) into 20mL tetrahydrofuran, stirring to dissolve the intermediate product B, slowly adding twice amount of potassium diphenylphosphate (20mmol), and carrying out reflux reaction at 85 ℃ for 40 h; after the reaction is finished, cooling the system to room temperature, carrying out rotary evaporation to recover tetrahydrofuran in the system, then soaking with 25ml of methanol, after solid is separated out, filtering and recovering the methanol, washing the solid with 5ml of methanol and 5ml of water in sequence, and carrying out vacuum drying to obtain a ligand L;
(4) adding the ligand L (3mmol) prepared in the step (3) into 20mL of dichloromethane solution, adding CuI (6mmol), and stirring at room temperature for 3 h; and after the reaction is finished, filtering, transferring the obtained solution to a small bottle, naturally volatilizing at room temperature for 80 hours to obtain a crude crystal, washing the crude crystal with methanol, and drying in vacuum to obtain the target copper complex, namely the benzimidazole diphosphine Cu (I) complex with the yield of 84%.
Effects of the embodiment
Characterization and detection are carried out on the benzimidazole diphosphine Cu (I) complex prepared in the embodiment 1-3:
(1) crystal structure
Under a microscope, selecting a benzimidazole diphosphine Cu (I) complex single crystal sample with proper size and smooth surface, and using a Bruker AMART APEX II CCD X-ray single crystal diffractometer to obtain Mo-Ka alpha through graphite at proper temperature
Figure BDA0002663572000000072
Collection sheetX-ray diffraction data and absorption correction using the multiple scanning procedure (SADABS). All structures were solved by direct method and refined by full matrix least squares based on F2 using SHELXTL package and Olex2 program. Hydrogen atoms are added at ideal positions and an anisotropic refinement is used for all non-hydrogen atoms. The crystal structure of the Cu (I) complex of benzimidazole diphosphine is shown in figure 1. Some of the parameters for crystallographic diffraction point data collection and structure refinement are shown in the following table:
TABLE 1 partial parameters for collection of data on crystallographic diffraction points and refinement of the Structure of the Benzoimidazolephosphonic Cu (I) complexes prepared in examples 1 to 3
Figure BDA0002663572000000071
Figure BDA0002663572000000081
(2) Ultraviolet-visible absorption spectroscopy
The ultraviolet-visible absorption spectrum analysis adopts a Perkin-Elmer Lambda 365 type ultraviolet-visible spectrometer for measurement, and the ligand L and the benzimidazole diphosphine Cu (I) complex are respectively dissolved in dichloromethane at room temperature to be prepared into the concentration of 1.0 multiplied by 10-5The measurement was carried out on the solution of mol/L, and the ultraviolet-visible absorption spectrum is shown in FIG. 2.
(3) Analysis of photoluminescence Properties
The emission spectrum analysis is carried out by adopting an F-4600 type fluorescence spectrometer, as shown in figure 3, wherein ex represents an excitation spectrum, em represents an emission spectrum, the maximum excitation wavelength of the benzimidazole diphosphine Cu (I) complex under the condition of 293K is 376nm, the maximum emission wavelength is 609nm, and the benzimidazole Cu (I) complex shows high-efficiency orange luminescence; the luminescence life is measured by an FLS980 type steady-state transient fluorescence spectrometer, and the life of the benzimidazole diphosphine Cu (I) complex solid powder reaches 2.26 mu s under the condition of 293K; 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 benzimidazole diphosphine Cu (I) complex solid powder under the condition of 293K reaches 45%.
(4) Nuclear magnetic characterization
The nuclear magnetic analysis of the intermediate compound A, B, the ligand L and the benzimidazole diphosphine Cu (I) complex prepared in the examples 1-3 is carried out by adopting a Br ker DPX-400MGHz superconducting nuclear magnetic resonance instrument.
Intermediate compound a:1H NMR(400MHz,Chloroform-d)δ8.52(s,1H),7.42(t,J＝7.8Hz,2H),7.31–7.19(m,4H),7.01(d,J＝8.8Hz,1H),6.66–6.55(m,1H).
intermediate compound B:1H NMR(400MHz,Chloroform-d)δ7.92(t,J＝1.6Hz,1H),7.55(dd,J＝7.8,1.8Hz,2H),7.53–7.43(m,6H),7.25–7.14(m,7H),7.06–6.96(m,4H).
ligand L:1H NMR(400MHz,Chloroform-d)δ7.64–7.60(m,1H),7.46–7.43(m,2H),7.42–7.39(m,6H),7.39–7.32(m,19H),7.21–7.04(m,10H),6.85–6.78(m,2H).31P NMR(162MHz,Chloroform-d)δ-17.97(s).
copper complex:1H NMR(400MHz,Chloroform-d)δ10.79(s,1H),7.80–7.75(m,8H),7.60–7.51(m,6H),7.45–7.31(m,20H),7.24(d,2H),6.91(d,J＝7.8,1.6Hz,2H),6.82–7.76(m,1H).31P NMR(162MHz,Chloroform-d)δ-32.57(s)。
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 Cu (I) complex of benzimidazole diphosphine, which is characterized in that the molecular formula is C56H40N4P2Cu2I2The structural formula is shown as formula I:
Figure FDA0002663571990000011
wherein Ph represents a phenyl group.
2. Cu (I) complex of benzimidazoledipine according to claim 1, characterized in that:
the structural unit of the benzimidazole diphosphine Cu (I) complex belongs to an orthorhombic system, the molecular weight is 1211.81, and the space group is Pna21The unit cell parameters are:
Figure FDA0002663571990000012
Figure FDA0002663571990000013
Figure FDA0002663571990000014
α＝90.00(3)°，γ＝90.00(3)°，β＝90.00(3)°。
3. cu (I) complex of benzimidazoledipine according to claim 1, characterized in that:
the benzimidazole diphosphine Cu (I) complex contains one dimer Cu in each complex molecule2(μ-I)2Unit, Cu due to narrow coordination space provided by ligand2(μ-I)2The unit is a micro-deformed plane quadrilateral configuration, the coordination environment around the Cu atom is a deformed tetrahedron configuration, and the central ion Cu and the N atom and the P atom on the ligand L form two stable five-membered chelate rings.
4. A process for the preparation of cu (i) complexes of benzimidazoles bisphosphines according to any of claims 1 to 3, characterized in that it comprises the following steps:
(1) adding aniline, 2, 6-difluoronitrobenzene and anhydrous potassium fluoride into a solvent, and reacting for 12-15 h at 95-100 ℃; purifying the product after the reaction is finished to obtain an intermediate product A;
(2) adding the intermediate product A prepared in the step (1), m-phthalaldehyde and sodium hydrosulfite into a mixed solvent, carrying out reflux reaction at 125-130 ℃ for 6-8 h, and purifying the product after the reaction is finished to obtain an intermediate product B;
(3) adding the intermediate product B prepared in the step (2) into a solvent, slowly adding potassium diphenylphosphate, carrying out reflux reaction at the temperature of 80-85 ℃ for 36-48 h, and purifying the 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 iodide, and stirring for 2-3 h at 20-35 ℃; and purifying the product after the reaction is finished to obtain the benzimidazole diphosphine Cu (I) complex.
5. The process for the preparation of Cu (I) complexes of benzimidazoles bisphosphines according to claim 4, characterized in that:
the structural formulas of the intermediate product A, the intermediate product B and the ligand L are shown as formulas II-IV;
Figure FDA0002663571990000021
wherein Ph represents a phenyl group.
6. The process for the preparation of Cu (I) complexes of benzimidazoles bisphosphines according to claim 4, characterized in that:
the molar ratio of the aniline, the 2, 6-difluoronitrobenzene and the anhydrous potassium fluoride in the step (1) is 1.2:1: 1.
7. The process for the preparation of Cu (I) complexes of benzimidazoles bisphosphines according to claim 4, characterized in that:
the molar ratio of the intermediate compound A, the m-phthalaldehyde and the sodium hydrosulfite in the step (2) is 2:1: 6.
8. The process for the preparation of Cu (I) complexes of benzimidazoles bisphosphines according to claim 4, characterized in that:
the molar ratio of the intermediate compound B to potassium diphenylphosphate in step (3) is 1: 2.
9. The process for the preparation of Cu (I) complexes of benzimidazoles bisphosphines according to claim 4, characterized in that:
and (4) the molar ratio of the ligand L to the cuprous iodide is 1: 2.
10. Use of the benzimidazole bisphosphine Cu (I) complex according to any one of claims 1 to 3 in the field of OLED luminescent materials.
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