CN106833008B

CN106833008B - Multidentate phosphine coordination silver complex dual-emitting dye, synthetic method and application thereof

Info

Publication number: CN106833008B
Application number: CN201710078385.7A
Authority: CN
Inventors: 许辉; 张静; 韩春苗
Original assignee: Heilongjiang University
Current assignee: Heilongjiang University
Priority date: 2017-02-14
Filing date: 2017-02-14
Publication date: 2020-05-22
Anticipated expiration: 2037-02-14
Also published as: CN106833008A

Abstract

A polydentate phosphine coordination silver complex double emission dye, a synthesis method and application thereof, the invention relates to a kind of multidentate phosphine coordination silver complex double emission dye, a synthesis method and application thereof. The purpose of the present invention is to solve the technical problem of poor device performance and stability caused by the quenching effect caused by the accumulation of phosphorescence and thermally excited delayed fluorescent dye excitons before, the dye is composed of a polydentate phosphine ligand and AgX coordination, The method is as follows: mix polydentate phosphine, AgX and DCM, react at 40°C for 1 hour, spin dry, dissolve in DCM, add H ₂ O ₂ in an ice-water bath, after 5 hours of reaction, extract with sodium bisulfite, take The lower layer is dried over anhydrous sodium sulfate, spin-dried and purified. The material has the characteristics of double emission, which minimizes the accumulation of excitons, improves device efficiency, and suppresses the roll-off of device efficiency. To achieve maximum utilization in the electroluminescence process.

Description

Multidentate phosphine coordination silver complex dual-emitting dye, synthetic method and application thereof

Technical Field

The invention relates to a polydentate phosphine coordination silver complex dual-emission dye, a synthetic method and application thereof.

Background

The high-efficiency and low-voltage driven organic electroluminescence brings revolutionary innovation to the development of the light emitting diode. The research on organic light emitting materials and devices has attracted much attention and intensive research. The organic electroluminescent diode is called as a third generation flat panel display and lighting technology, has outstanding advantages in the aspects of energy saving, environmental protection and the like, and in order to effectively utilize singlet excitons and triplet excitons generated in the electroluminescent process, a commonly adopted mode at present is to use phosphorescent dyes to construct electrophosphorescence, but the types of phosphorescent materials are limited, and other materials are strictly needed to be used for replacing the electrophosphorescence due to the severe quenching effect. Recently, a thermally-excited delayed fluorescence technology, which is called a third-generation organic electroluminescence technology, has been greatly developed, in which a thermally-excited delayed fluorescence dye can convert triplet excitons into singlet excitons through an inverse gap transition from the triplet state to the singlet state thereof, and then emit light using the same, thereby theoretically achieving an internal quantum efficiency of 100%. Delay of thermal excitationFluorescent (TADF) compounds are currently under intense investigation because such materials can be achieved by cu (i) complexes, as well as purely organic molecules. There are few reports on TADF materials based on ag (i). This is because Ag + ions have a higher oxidation potential than Cu + ions, and thus d¹⁰Ag (i) metal complexes do not typically exhibit TADF. Because of d¹⁰The metal complex has a complete d orbit, and few silver complexes have the characteristics of thermal excitation delayed fluorescence and phosphorescence double emission, and the main reason is that the effective phosphorescence emission is difficult to obtain due to the weak spin-orbit coupling between silver ions and ligands in the silver complexes, but at present, the silver complexes still do not develop a double-emission electroluminescent dye and provide a very good platform. The work not only embodies the convincing superiority of the dual-emission material in the aspect of exciton utilization rate, but also proves that a feasible way for modulating the emission ratio is feasible, and lays a good foundation for the further development and application of the light-emitting material.

Disclosure of Invention

The invention aims to solve the technical problem of poor device performance and stability caused by quenching effect caused by exciton accumulation of phosphorescent and thermally excited delayed fluorescent dyes in the prior art, and provides a multidentate phosphine-coordinated silver complex dual-emitting dye, a synthetic method and application thereof.

The polydentate phosphine coordination silver complex dual-emission dye is formed by coordination of a polydentate phosphine ligand and AgX, and the general formula of the molecular structure is as follows:

the multidentate phosphine ligand is DPPPPPO, DPNAPO or DPAPO, wherein X is Cl, Br or I.

The dye synthesis method comprises the following steps:

firstly, mixing 1mmol of bidentate phosphine, 0.5-1 mmol of AgX and 5-10 ml of DCM, reacting for 1 hour at 40 ℃, and then spin-drying, wherein the bidentate phosphine is DPPPP, DPNAP or DPAP, X is Cl, Br or I, and DPPPPAgX, DPNAPAgX or DPAPAgX is obtained;

secondly, dissolving 1mmol of DPPPPAgX, DPNAPAgX or DPAPAgX in DCM, and adding 5-10 mmol of H in ice-water bath₂O₂And after 5 hours of reaction, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with a mixed solvent of ethyl acetate and ethanol as an eluent to obtain the polydentate phosphine coordination silver complex.

The ratio of the multidentate phosphine ligand to AgX is (1-2) to 1.

The DPPPPAgX, DPNAPAgX or DPAPAgX and H₂O₂The ratio of the amounts of (1) to (2) was 1: 1.

The volume ratio of Ethyl Acetate (EA) to ethanol (EtOH) in the mixed solvent of ethyl acetate and ethanol is 1: 10.

The multidentate phosphine-coordinated silver complex dual-emitting dye is used as a light-emitting layer for preparing an electroluminescent device.

The polydentate phosphine coordination silver complex dual-emission dye has the characteristic of dual emission, can emit thermal excitation delayed fluorescence and also can emit phosphorescence, and can simultaneously utilize singlet excitons and triplet excitons as the singlet and triplet states can be simultaneously transited, and realize dynamic distribution of the excitons in the electroluminescent process, so that the accumulation of the excitons is reduced to the maximum extent, the efficiency of a device is improved, the efficiency roll-off of the device is inhibited, and the maximum utilization in the electroluminescent process is realized. In the invention, the multidentate coordination is utilized to increase the spin-orbit coupling of the ligand to the metal, and the charge transfer from the halogen to the ligand is regulated by the halogen, so that the phosphorescence emission of the silver complex is enhanced, and finally, the dual-emission performance of both thermally-excited delayed fluorescence and phosphorescence is obtained. Meanwhile, the conjugation degree of the ligand is increased by adding the benzene ring, so that the luminescent color of the silver complex is adjusted. The multidentate phosphine-coordinated silver complex dual-emitting dye electroluminescent guest material prepared by the invention can realize an ultra-low voltage driven high-efficiency thermally-excited delayed fluorescence device, and the current efficiency of the high-efficiency thermally-excited delayed fluorescence device reaches the maximum value of 21.2 cd.A^-1The external quantum efficiency reaches a maximum of 21%.

The multidentate phosphine-coordinated silver complex dual-emission dye electroluminescent guest material used for electroluminescent devices has the following advantages:

1. can be used as a guest for a light-emitting layer of an electroluminescent device.

2. The performance of the electroluminescent device material is improved, the starting voltage of the electroluminescent device is reduced to 3.2V by the electroluminescent device prepared from the multidentate phosphine-silver complex double-emitting dye guest material, the electroluminescent device has good thermodynamic stability, the cracking temperature is 338-446 ℃, and meanwhile, the luminous efficiency and brightness of the organic electroluminescent material are improved.

Drawings

FIG. 1 is a UV fluorescence spectrum of a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, a fluorescence spectrum and a phosphorescence spectrum dissolved in a dichloromethane solvent, ■ ● ▲ respectively shows the UV spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, □ ○△ respectively shows the fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three dissolved in a dichloromethane solvent, and it ★◇ respectively shows the phosphorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three;

FIG. 2 is a thermogravimetric analysis diagram of a multidentate phosphine-coordinated silver complex dual-emission dye in experiment one, experiment two and experiment three, and ■◆▲ is a thermogravimetric analysis diagram of the multidentate phosphine-coordinated silver complex dual-emission dye in experiment one, experiment two and experiment three, respectively;

FIG. 3 is a voltage-current density relationship curve of an electroluminescent device with a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, wherein ■ ● ▲ in the graph respectively shows the voltage-current density relationship curve of the electroluminescent device with the multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three;

FIG. 4 is a voltage-luminance relationship curve of an electroluminescent device with a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, wherein ■ ● ▲ in the graph respectively shows the voltage-luminance relationship curve of the electroluminescent device with the multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three;

FIG. 5 is a graph showing the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, wherein ■ ● ▲ shows the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, respectively;

FIG. 6 is a graph showing the relationship between luminance and power efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, wherein ■ ● ▲ shows the relationship between luminance and power efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, respectively;

FIG. 7 is the current density-external quantum efficiency curve efficiency of the electroluminescent device with multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three, wherein ■ ● ▲ in the graph respectively represents the current density-external quantum efficiency curve efficiency of the electroluminescent device with multidentate phosphine-coordinated silver complex dual-emitting dye in experiment one, experiment two and experiment three;

FIG. 8 is the electroluminescence spectra of the electroluminescence devices of multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment one, experiment two and experiment three, wherein ■ ● ▲ in the figure respectively shows the electroluminescence spectra of the electroluminescence devices of multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment one, experiment two and experiment three;

FIG. 9 is a UV fluorescence spectrum of multidentate phosphine-coordinated silver complex dual-emitting dye in experiment four, experiment five and experiment six, a fluorescence spectrum and a phosphorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye dissolved in dichloromethane solvent, ■ ● ▲ respectively shows a UV spectrum of multidentate phosphine-coordinated silver complex dual-emitting dye in experiment four, experiment five and experiment six, □ ○△ respectively shows a fluorescence spectrum of multidentate phosphine-coordinated silver complex dual-emitting dye dissolved in dichloromethane solvent in experiment four, experiment five and experiment six, and it ★◇ respectively shows a phosphorescence spectrum of multidentate phosphine-coordinated silver complex dual-emitting dye in experiment four, experiment five and experiment six;

FIG. 10 is a thermogravimetric analysis chart showing multidentate phosphine-coordinated silver complex dual-emission dyes in experiment four, experiment five and experiment six, and ■◆▲ is a thermogravimetric analysis chart showing multidentate phosphine-coordinated silver complex dual-emission dyes in experiment four, experiment five and experiment six, respectively;

FIG. 11 is a graph showing voltage-current density relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, wherein ■ ● ▲ shows the voltage-current density relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, respectively;

FIG. 12 is a graph showing the voltage-luminance relationship of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, wherein ■ ● ▲ shows the voltage-luminance relationship of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, respectively;

FIG. 13 is a graph showing the relationship between luminance and current efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, wherein ■ ● ▲ shows the relationship between luminance and current efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, respectively;

FIG. 14 is a graph showing the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, wherein ■ ● ▲ shows the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, respectively;

FIG. 15 is the current density-external quantum efficiency curve efficiencies of the electroluminescent devices with multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, wherein ■ ● ▲ represents the current density-external quantum efficiency curve efficiencies of the electroluminescent devices with multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment four, experiment five and experiment six, respectively;

FIG. 16 is the electroluminescent spectrum of the electroluminescent device with multidentate phosphine-coordinated silver complex dual-emitting dye in experiment four, experiment five and experiment six, wherein ■ ● ▲ shows the electroluminescent spectrum of the electroluminescent device with multidentate phosphine-coordinated silver complex dual-emitting dye in experiment four, experiment five and experiment six, respectively;

FIG. 17 is a UV fluorescence spectrum of multidentate phosphine-coordinated silver complex dual-emission dye in seven, eight and nine experiments, a fluorescence spectrum and a phosphorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emission dye dissolved in dichloromethane solvent, ■ ● ▲ respectively shows a UV spectrum of multidentate phosphine-coordinated silver complex dual-emission dye in seven, eight and nine experiments, □ ○△ respectively shows a fluorescence spectrum of multidentate phosphine-coordinated silver complex dual-emission dye dissolved in dichloromethane solvent in seven, eight and nine experiments, and it ★◇ respectively shows a phosphorescence spectrum of multidentate phosphine-coordinated silver complex dual-emission dye in seven, eight and nine experiments;

FIG. 18 is a thermogravimetric analysis chart showing multidentate phosphine-coordinated silver complex dual-emission dyes in experiment seven, experiment eight and experiment nine, and ■◆▲ is a thermogravimetric analysis chart showing multidentate phosphine-coordinated silver complex dual-emission dyes in experiment seven, experiment eight and experiment nine, respectively;

FIG. 19 is a graph showing voltage-current density relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● ▲ shows the voltage-current density relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, respectively;

FIG. 20 is a graph showing voltage-luminance relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● ▲ shows the voltage-luminance relationship curves of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, respectively;

FIG. 21 is a graph showing the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment seven, experiment eight or experiment nine, wherein ■ ● ▲ shows the relationship between luminance and current efficiency of an electroluminescent device using a multidentate phosphine-coordinated silver complex dual-emitting dye in experiment seven, experiment eight or experiment nine, respectively;

FIG. 22 is a graph showing the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● ▲ shows the relationship between luminance and power efficiency of electroluminescent devices using multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, respectively;

FIG. 23 is the current density-external quantum efficiency curve efficiencies of electroluminescent devices with multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine, wherein ■ ● ▲ in the figure respectively shows the current density-external quantum efficiency curve efficiencies of electroluminescent devices with multidentate phosphine-coordinated silver complex dual-emitting dyes in experiment seven, experiment eight and experiment nine;

fig. 24 is an electroluminescence spectrum of an electroluminescence device of a multidentate phosphine-coordinated silver complex double-emitting dye in experiment seven, experiment eight and experiment nine, and ■ ● ▲ in the diagram respectively shows the electroluminescence spectrum of the electroluminescence device of the multidentate phosphine-coordinated silver complex double-emitting dye in experiment seven, experiment eight and experiment nine.

FIGS. 25 to 33 are graphs of the temperature-changing lifetime of 80K to 300K of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in the first to ninth experiments, and it can be seen from each graph that: the lifetime is sharply decreased with increasing temperature, phosphorescent emission at low temperature, and thermal excitation delayed fluorescence property is exhibited with increasing temperature, thereby exhibiting dual emission.

Detailed Description

The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.

The first embodiment is as follows: the polydentate phosphine coordination silver complex dual-emission dye is formed by coordination of a polydentate phosphine ligand and AgX, and the general formula of the molecular structure is as follows:

The second embodiment is as follows: the method for synthesizing the bidentate phosphine coordination silver complex dual-emission dye is characterized by comprising the following steps of:

The third concrete implementation mode: the present embodiment is different from the second embodiment in that the ratio of the multidentate phosphine ligand to AgX is (1 to 2): 1. The rest is the same as the second embodiment.

The fourth concrete implementation mode: the second or third difference between the present embodiment and the present embodiment is that the dppppaggx, DPNAPAgX or DPAPAgX and H₂O₂The ratio of the amounts of (1) to (2) was 1: 1. The other is the same as the second or third embodiment.

The fifth concrete implementation mode: the difference between this embodiment and one of the second to fourth embodiments is that the PPPPPPPGX, DPNAPAGX or DPAPAgX and H₂O₂The ratio of the amounts of the components is 1: 2. The other is the same as one of the second to fourth embodiments.

The sixth specific implementation mode: this embodiment is different from the second to fifth embodiments in that the volume ratio of ethyl acetate to ethanol in the mixed solvent of ethyl acetate and ethanol is 1: 10. The other is the same as one of the second to fifth embodiments.

The seventh embodiment: this embodiment differs from one of the second to sixth embodiments in that in step one 1mmol of the polydentate phosphine ligand, 0.7mmol of AgX and 7ml of DCM are mixed. The other is the same as one of the second to sixth embodiments.

The specific implementation mode is eight: this embodiment differs from one of the second to seventh embodiments in that in step one 1mmol of the polydentate phosphine ligand, 0.8mmol of AgX and 8ml of DCM are mixed. The rest is the same as one of the second to seventh embodiments.

The specific implementation method nine: the difference between this embodiment and the second to eighth embodiment is that 6mmol H is added in the second step under ice-water bath₂O₂. The rest is the same as the first to eighth embodiments.

The detailed implementation mode is ten: detailed description of the inventionthe bidentate phosphine-silver complex dual emission dye is used as a light emitting layer for the preparation of an electroluminescent device.

The method for preparing the electrophosphorescent device by using the multidentate phosphine-coordinated silver complex dual-emitting dye as a light-emitting layer in the embodiment is as follows:

firstly, putting the glass or plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10^-6mbar, setting evaporation rate at 0.1-0.3 nm s^-1Evaporating an anode conducting layer which is made of Indium Tin Oxide (ITO) and has the thickness of 1-100 nm on a glass or plastic substrate;

secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a hole injection layer with the thickness of 2-10 nm;

thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 20-40 nm;

fourthly, evaporating and plating a bidentate phosphine coordination silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain a mixture with the thickness of 5-15 nm;

fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 10-80 nm;

sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 1-10 nm;

and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 1-100 nm on the electron injection layer to obtain the electroluminescent device.

And seventhly, the metal is calcium, magnesium, silver, aluminum, calcium alloy, magnesium alloy, silver alloy or aluminum alloy.

The following experiments are adopted to verify the effect of the invention:

experiment one: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then spin-dried to obtain DPPPPAgCl.

The resulting 1mmol of DPPPPPAgCl was dissolved in DCM and 10mmol of H was added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgCl ratio is 1: 1.

The DPPPPAgCl and H₂O₂The ratio of the amounts of the components is 1: 2.

The volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment has the structural formula

The polydentate phosphine coordination silver complex dual-emitting dye obtained by the experiment is DPPPPOAgCl.

The nuclear magnetic resonance spectrometer is adopted to detect the multifunctional modified DPPPPPOAgCl prepared in the test, and the detection result is as follows:

¹H NMR(TMS,CDCl₃,400MHz):＝8.018(t,J＝7.6Hz,2H),7.742(t,J＝7.6Hz,2H),7.667(s,2H),7.602(d,J＝6.8Hz,1H),7.380-6.885(m,34H),6.808-6.733(m,2H),6.649(d,J＝6.8Hz,2H),6.530-6.489ppm(m,1H)；LDI-TOF:m/z(％):1002(100)[M⁺]；elementalanalysis(％)for C₅₆H₄₆AgClOP₄:C,67.11；H,4.63；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgCl, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgCl obtained by the experiment is shown in figure 2, and the graph shows that the cracking temperature of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgCl is 425 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgCl as a luminescent layer comprises the following steps:

firstly, putting the plastic substrate cleaned by deionized water into a vacuum evaporation plating instrument with the vacuum degree of 1 multiplied by 10^-6mbar, evaporation rate set at 0.1nm s^-1An anode conducting layer with the thickness of 10nm is formed on a glass or plastic substrate by vapor deposition of Indium Tin Oxide (ITO);

secondly, evaporating a hole injection layer material MoOx on the anode conducting layer to obtain a 10 nm-thick hole injection layer;

thirdly, evaporating a hole transport layer material TAPC on the hole injection layer to obtain a hole transport layer with the thickness of 40 nm;

fourthly, evaporating and plating a bidentate phosphine coordination silver complex dual-emission dye on the hole transport layer to be mixed with a main material mCP to obtain the material with the thickness of 15 nm;

fifthly, evaporating and plating an electron transport layer material TPBi on the light-emitting layer, wherein the thickness of the electron transport layer material TPBi is 80 nm;

sixthly, evaporating and plating an electron injection layer material LiF on the electron transport layer, wherein the thickness of the electron injection layer is 10 nm;

and seventhly, evaporating a cathode conducting layer which is made of metal and has the thickness of 10nm on the electron injection layer to obtain the electrophosphorescent device.

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPPPOAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 3, and the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl material has semiconductor characteristics and threshold value thereofThe voltage was 3.7V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgCl in the experiment is shown in FIG. 4, and the figure shows that the starting voltage of the device is 3.8V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 21.1 cd.A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in FIG. 6, and the graph shows that the device has the brightness of 2 cd.m^-2When the power efficiency reaches the maximum value of 16.2 lm.W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 7, and the graph shows that the device has the brightness of 0.3 mA-cm^-2Then, a maximum external quantum efficiency of 8% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgCl in the experiment is shown in figure 8, and the electroluminescence peak of the device is at 603 nm. Fig. 25 is a graph of the 80K-300K temperature-variable lifetime of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in the first experiment, and it can be seen from the graph that the lifetime is sharply decreased with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Experiment two: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then dried in a spinning mode to obtain the DPPPPAgBr.

The resulting 1mmol of DPPPPPAgBr was dissolved in DCM and 10mmol of H was added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the ratio of multidentate phosphine ligand to AgBr is 1: 1.

The DPPPPAgBr and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The polydentate phosphine coordination silver complex dual-emitting dye obtained by the experiment is DPPPPOAgBr.

The nuclear magnetic resonance apparatus is adopted to detect the multifunctional modified DPPPPPOAgBr prepared in the test, and the detection result is as follows:

¹H NMR(TMS,CDCl₃,400MHz):＝7.992(t,J＝8Hz,2H),7.745(t,J＝7.2Hz,2H),7.641(s,2H),7.589(d,J＝6.4Hz,1H),7.373-7.147(m,21H),7.082-6.881(m,13H),6.808(s,1H),6.729-6.657(m,3H),6.557-6.517ppm(m,1H)；LDI-TOF:m/z(％):1046(100)[M⁺]；elemental analysis(％)for C₅₆H₄₆AgBrOP₄:C,64.26；H,4.43；

the experiment obtains the ultraviolet fluorescence spectrum of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr obtained in the experiment is shown in figure 2, and the graph shows that the cracking temperature of the polydentate phosphine coordination silver complex dual-emission dye DPPPPOAgBr is 433 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgBr as the luminescent layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPPPOAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 3, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr material has semiconductor characteristics, and the threshold voltage of the material is 3.7V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 4, and the figure shows that the starting voltage of the device is 3.8V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 21cd & A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 6, and the graph shows that the device has the brightness of 5 cd.m^-2When the power efficiency reaches the maximum value of 11 lm.W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 7From this figure, it is found that the device has a luminance of 0.6mA cm^-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgBr in the experiment is shown in figure 8, and the electroluminescence peak of the device is shown at 605 nm. FIG. 26 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment two, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Experiment three: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed, reacted at 40 ℃ for 1 hour, and then spin-dried to obtain DPPPPAgI.

The resulting 1mmol of DPPPPPAgI was dissolved in DCM and 10mmol of H was added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPPPPAgI and the DPPPPAgI H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPPPPOAgI.

The nuclear magnetic resonance apparatus is adopted to detect the multifunctional modified DPPPPPOAgI prepared by the test, and the detection result is as follows:

¹H NMR(TMS,CDCl₃,400MHz):＝7.928(t,J＝7.6Hz,2H),7.736(t,J＝8Hz,2H),7.604(d,J＝8Hz,4H),7.443-7.238(m,15H),7.212-7.015(m,13H),6.969-6.824(m,6H),6.705(s,3H),6.565ppm(t,J＝8Hz,1H)；LDI-TOF:m/z(％):1093(100)[M⁺]；elementalanalysis(％)for C₅₆H₄₆AgIOP₄:C,61.50；H,4.24；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI, and the phosphorescence spectrum is shown in figure 1. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI obtained in the experiment is shown in figure 2, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI is 437 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgI as a luminescent layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPPPPOAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI in the experiment is shown in figure 3, and therefore, the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPPOAgI material has semiconductor characteristics and the threshold voltage of the material is 3.5V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 4, and the figure shows that the starting voltage of the device is 3.7V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 5, and the graph shows that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 21cd & A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in FIG. 6, and the graph shows that the device has the brightness of 6 cd.m^-2When the power efficiency reaches the maximum value of 16lm W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPPPPOAgI in the experiment is shown in figure 7, and the graph shows that the device has the brightness of 0.6 mA-cm^-2Then, a maximum external quantum efficiency of 8.1% was obtained. The electroluminescence spectrum of the electroluminescence device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPPPPOAgI in the experiment is shown in figure 8, and the electroluminescence peak of the device is at 602 nm. FIG. 27 is a graph of the 80K-300K temperature-variable lifetime of the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment III, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Experiment four: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM were mixed, reacted at 40 ℃ for 10 hours, and then spin-dried to obtain DPNAPAAgCl.

The resulting 1mmol of DPNAPAAgCl was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPNAPAAgCl and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The polydentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGCl.

The multifunctional modified DPNAPAOGCl prepared by the test is detected by mass spectrum, and the detection result is as follows:

m/z:575.09(100.0％),576.09(92.9％),575.59(73.5％),576.59(68.3％),576.08(32.0％),577.08(29.7％),576.09(26.6％),577.09(24.8％),576.59(23.5％),577.59(21.8％),578.09(7.7％),577.09(7.2％),577.59(5.7％),576.59(4.6％),577.59(2.0％),578.59(1.9％),576.59(1.8％),577.09(1.3％),577.09(1.1％),578.09(1.0％)；LDI-TOF:m/z(％):1152(100)[M⁺]，Elemental Analysis for C₆₈H₅₂AgClOP₄:C,70.88；H,4.55；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGCl, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPOAgCl obtained in the experiment is shown in fig. 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPOAgCl is 338 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl as a light-emitting layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPNAPAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in figure 11, so that the graph shows that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl material has semiconductor characteristics, and the threshold voltage of the material is 4V. The voltage-luminance relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl in the experiment is shown in FIG. 12, and the figure shows that the starting voltage of the device is 4V. FIG. 13 shows the luminance-current efficiency relationship curve of the electroluminescent device prepared from DPNAPAAGCl as a multidentate phosphine-coordinated silver complex dual-emitting dye, and it can be seen from the graph that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 11.7 cd.A^-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in FIG. 14, and the graph shows that the device has the luminance of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 60lm W^-1. The current density-external quantum efficiency relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGCl in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm^-2Then, a maximum external quantum efficiency of 21% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAgCl in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is 611 nm. FIG. 28 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment IV, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Experiment five: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a rotary manner to obtain DPNAPAAgBr.

The resulting 1mmol of DPNAAgBr was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPNAAgBr and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The polydentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGBr.

The multifunctional modified DPNAPAOGBr prepared in the test is detected by mass spectrum, and the detection result is as follows:

m/z:597.06(100.0％),598.06(97.3％),598.06(92.9％),599.06(90.4％),597.56(73.5％),598.56(71.5％),598.56(68.3％),599.56(66.5％),598.06(26.6％),599.06(24.8％),599.06(24.3％),600.06(23.9％),598.57(6.3％),599.56(6.2％),599.57(5.9％),600.56(5.7％),599.06(1.6％),599.07(1.1％),600.07(1.0％)；LDI-TOF:m/z(％):1192(100)[M⁺]，Elemental Analysis for C₆₈H₅₂AgBrOP₄:C,68.24；H,4.38；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAAgBr, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGBr obtained in the experiment is shown in figure 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGBr is 424 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr as a light-emitting layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPNAPAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGBr in the experiment is shown in figure 11, so that the graph shows that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAGBr material has semiconductor characteristics, and the threshold voltage of the material is 3.9V. The voltage-brightness relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in figure 12, and the figure shows that the starting voltage of the device is 3.9V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 13, and the graph shows that the device has the luminance of 2.5 cd.m^-2When the current efficiency reaches the maximum value of 9 cd. A^-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 14, and the graph shows that the device has the luminance of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 47.7 lm.W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm^-2Then, a maximum external quantum efficiency of 20.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgBr in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is at 612 nm. FIG. 29 shows the multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment fiveThe 80K-300K temperature-variable lifetime spectrum of the material shows that the lifetime is sharply reduced along with the temperature rise, phosphorescence emission is realized at low temperature, and thermal excitation delayed fluorescence is realized along with the temperature rise, so that double emission is realized.

Experiment six: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, followed by spin-drying and spin-drying to obtain DPNAPAAgI.

The resulting 1mmol of DPNAPAAgI was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPNAAgI and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPNAPAOGI.

The multifunctional modified DPNAPOAgI prepared in the test is detected by mass spectrometry, and the detection result is as follows:

m/z:621.05(100.0％),622.05(92.9％),621.56(73.5％),622.56(68.3％),622.06(26.6％),623.06(24.8％),623.56(5.7％),622.56(4.6％),622.56(1.8％),623.06(1.1％),624.06(1.0％)；LDI-TOF:m/z(％):1243(100)[M⁺]，Elemental Analysisfor C₆₈H₅₂AgIOP₄:C,65.66；H,4.21

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOGI, and the phosphorescence spectrum is shown in figure 9. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOAgI obtained in the experiment is shown in figure 10, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emitting dye DPNAPAOAgI is 446 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAAgI as a light-emitting layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPNAPAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in figure 11, so that the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI material has semiconductor characteristics, and the threshold voltage of the material is 3.8V. The experiment is carried out by preparing multidentate phosphine coordination silver complex dual-emitting dye DPNAPAOGIThe voltage-luminance relationship curve of the electroluminescent device is shown in fig. 12, and the starting voltage of the device is 3.8V. FIG. 13 shows the luminance-current efficiency relationship curve of the electroluminescent device prepared from DPNAPAOGI, which is a multidentate phosphine-coordinated silver complex dual-emitting dye, and it can be seen from the graph that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 13.4 cd.A^-1. The graph of the relationship between luminance and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in FIG. 14, and the graph shows that the device has the luminance of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 70.7 lm.W^-1. The current density-external quantum efficiency relationship curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in figure 15, and the graph shows that the device has the brightness of 6 mA-cm^-2Then, a maximum external quantum efficiency of 19.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPNAPAOGI in the experiment is shown in FIG. 16, and the electroluminescent peak of the device is 621 nm. FIG. 30 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment six, and it can be seen from the graph that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Experiment seven: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgCl and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the reaction product is dried in a spinning mode to obtain DPAPAgCl.

The resulting 1mmol of DPAPAgCl was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPAPAgCl and H₂O₂The ratio of the amounts of the components is 1: 2.

The volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgCl.

The mass spectrum is adopted to detect the multifunctional modified DPAPOAgCl prepared by the test, and the detection result is as follows:

m/z:650.11(100.0％),651.11(92.9％),650.61(86.5％),651.61(80.4％),651.11(37.0％),652.11(34.3％),651.11(32.0％),652.11(29.7％),651.61(27.7％),652.61(25.7％),652.11(11.8％),653.11(11.0％),652.61(9.7％),651.61(7.1％),651.61(3.3％),653.61(2.7％),652.61(2.3％),653.12(1.5％),652.12(1.2％),652.61(1.1％；LDI-TOF:m/z(％):1302(100)[M⁺]，Elemental Analysis for C₈₀H₅₈AgClOP₄:C,73.77；H,4.49；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgCl obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgCl is 389 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgCl as a luminescent layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPOAgCl (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 19, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 20, and the figure shows that the starting voltage of the device is 3.4V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 21, and the graph shows that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 11.6 cd.A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in FIG. 22, and the graph shows that the device has the brightness of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 5.7 lm.W^-1. The experiment shows that the current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine coordination silver complex dual-emitting dye DPAPOAgClThe line is shown in FIG. 23, from which it is clear that the device has a luminance of 6mA cm^-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgCl in the experiment is shown in figure 24, and the electroluminescent peak of the device is known to be at 607 nm. FIG. 31 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment seven, and it can be seen from the graph that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is displayed with the increase of temperature, so that dual emission is reflected.

Experiment eight: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgBr and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a spinning mode to obtain DPAPAgBr.

The resulting 1mmol of DPAPAgBr was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPAPAgBr and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

Performing column chromatography purification by taking DCM and PE as eluent to obtain a multidentate phosphine coordination silver complex;

wherein the ratio of multidentate phosphine ligand to AgBr is 1: 1.

The volume ratio of the DCM to the PE in the mixed solvent of the DCM and the PE is 1: 20.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgBr.

The mass spectrum is adopted to detect the multifunctional modified DPAPOAgBr prepared by the test, and the detection result is as follows:

m/z:672.08(100.0％),673.08(97.3％),673.08(92.9％),674.08(90.4％),672.59(86.5％),673.58(84.2％),673.59(80.4％),674.58(78.2％),674.09(36.0％),675.09(33.4％),674.09(26.2％),673.09(24.2％),673.09(12.8％),674.59(9.3％),674.09(8.1％),675.59(6.2％),674.59(5.9％),673.59(5.8％),674.59(4.2％),675.59(3.2％),673.59(2.5％),673.59(2.1％),675.09(1.8％),674.09(1.5％),675.09(1.1％),676.09(1.0％)；LDI-TOF:m/z(％):1347(100)[M⁺]，Elemental Analysis forC₈₀H₅₈AgBrOP₄:C,71.33；H,4.34；

the experiment obtains the ultraviolet fluorescence spectrum of the polydentate phosphine coordination silver complex dual-emission dye DPAPOAgBr, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgBr obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgBr is 396 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgBr as the luminescent layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPOAgBr (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 19, so that the graph shows that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. The voltage-brightness relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 20, and the figure shows that the starting voltage of the device is 3.5V. The graph of the relationship between brightness and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 21, and the graph shows that the device has the brightness of 2.5 cd.m^-2When the current efficiency reaches the maximum value of 12.3 cd.A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 22, and the graph shows that the device has the brightness of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 6.7 lm.W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 23, and the graph shows that the device has the brightness of 6 mA-cm^-2Then, a maximum external quantum efficiency of 8% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgBr in the experiment is shown in figure 24, and the electroluminescent peak of the device is at 602 nm. FIG. 32 is a graph showing the multidentate phosphine-coordinated copper complex dual emission electroluminescence in experiment eightThe graph shows that the service life of the luminescent dye is sharply reduced along with the temperature rise, the luminescent dye is phosphorescent emission at low temperature, and the luminescent dye shows thermal excitation delay fluorescence property along with the temperature rise, so that dual emission is realized.

Experiment nine: the synthesis method of the experimental multidentate phosphine-coordinated silver complex dual-emitting dye is realized according to the following steps:

1mmol of polydentate phosphine, 1mmol of AgI and 5ml of DCM are mixed and reacted at 40 ℃ for 10 hours, and then the mixture is dried in a spinning mode to obtain DPAPAgI.

The resulting 1mmol of DPAPAgI was dissolved in DCM and 10mmol of H were added under ice-water bath₂O₂And after reacting for 5 hours, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with EA and EtOH as eluent to obtain the polydentate phosphine coordination silver complex.

Wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The DPAPAgI and H₂O₂The amount ratio of (A) to (B) is 1: 2.

the volume ratio of EA to EtOH in the mixed solvent of EA and EtOH is 1: 10.

wherein the multidentate phosphine ligand to AgI ratio is 1: 1.

The multidentate phosphine-coordinated silver complex dual-emitting dye obtained by the experiment is DPAPOAgI.

The mass spectrum is adopted to detect the multifunctional modified DPAPOAgI prepared by the test, and the detection result is as follows:

m/z:696.08(100.0％),697.08(92.9％),696.58(86.5％),697.58(80.4％),697.08(37.0％),698.08(34.3％),698.58(8.3％),697.58(7.1％),697.58(3.3％),699.08(1.5％),698.58(1.4％),698.08(1.2％)；LDI-TOF:m/z(％):1347(100)[M⁺]，Elemental Analysis for C₈₀H₅₈AgIOP₄:C,68.93；H,4.19；

the experiment obtains the ultraviolet fluorescence spectrum of the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI, and the phosphorescence spectrum is shown in figure 17. The thermogravimetric analysis spectrogram of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgI obtained in the experiment is shown in fig. 18, and the graph shows that the cracking temperature of the multidentate phosphine-coordinated silver complex dual-emission dye DPAPOAgI is 419 ℃.

The method for preparing the electroluminescent device by using the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgI as a light-emitting layer comprises the following steps:

And seventhly, the metal is aluminum.

The structure of the experimental electrophosphorescent device is as follows: ITO/MoOx (10nm)/TAPC (40nm)/mCP DPAPOAgI (15nm)/TPBi (80nm)/LiF (10 nm)/Al.

The voltage-current density relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgBr in the experiment is shown in figure 19, so that the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI material has semiconductor characteristics, and the threshold voltage of the material is 3.2V. In this experiment, the multidentate phosphine was coordinated, and it can be seen from FIG. 20 that the turn-on voltage of the device was 3.5V. The graph of the relationship between luminance and current efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in FIG. 21, and the graph shows that the luminance of the device is 2.5 cd.m^-2When the current efficiency reaches the maximum value of 12.7 cd.A^-1. The graph of the relationship between brightness and power efficiency of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in FIG. 22, and the graph shows that the device has the brightness of 2.1 cd.m^-2When the power efficiency reaches the maximum value of 6.7 lm.W^-1. The current density-external quantum efficiency relation curve of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex dual-emitting dye DPAPOAgI in the experiment is shown in figure 23, and the graph shows that the device has the brightness of 6 mA-cm^-2Then, a maximum external quantum efficiency of 8.2% was obtained. The electroluminescence spectrum of the electroluminescent device prepared by the multidentate phosphine-coordinated silver complex double-emitting dye DPAPOAgI in the experiment is shown in figure 24, and the electroluminescent peak of the device is at 608 nm. FIG. 33 is a graph of the 80K-300K temperature-variable lifetime of a multidentate phosphine-coordinated copper complex dual-emitting electroluminescent dye in experiment nine, from which it can be seen that the lifetime is sharply reduced with the increase of temperature, phosphorescence emission is performed at low temperature, and thermal excitation delayed fluorescence is exhibited with the increase of temperature, thereby embodying dual emission.

Claims

1. The application of the multidentate phosphine-coordinated silver complex dual-emitting dye is characterized in that,

the multidentate phosphine-coordinated silver complex dual-emitting dye is used as a luminescent layer for preparing an electroluminescent device,

the dye is formed by coordination of a multidentate phosphine ligand and AgX, and the general formula of the molecular structure is as follows:

the polydentate phosphine ligand is DPNAPO, wherein X is Cl, Br or I.

2. Use of a multidentate phosphine-coordinated silver complex birefrigent dye according to claim 1, wherein the dye is synthesized by the following method:

firstly, mixing 1mmol of polydentate phosphine, 0.5-1 mmol of AgX and 5-10 ml of DCM, reacting at 40 ℃ for 1 hour, and then spin-drying, wherein the polydentate phosphine is DPNAP, and X is Cl, Br or I to obtain DPNAPAAgX;

secondly, dissolving 1mmol of DPNAPAAgX in DCM, and adding 5-10 mmol of H in ice-water bath₂O₂And after 5 hours of reaction, extracting with sodium bisulfite, taking the lower layer, drying with anhydrous sodium sulfate, spin-drying, and purifying by column chromatography with a mixed solvent of ethyl acetate and ethanol as an eluent to obtain the polydentate phosphine coordination silver complex.

3. The use of a multidentate phosphine-coordinated silver complex biradiant dye as claimed in claim 2, wherein the ratio of multidentate phosphine to AgX is (1-2) to 1.

4. The use of a polydentate phosphine-coordinated silver complex bis-emissive dye as defined in claim 2, wherein said DPNAPAgX is in combination with H₂O₂The mass ratio of (1) - (2).

5. The use of a polydentate phosphine-coordinated silver complex bis-emissive dye as defined in claim 2, wherein said DPNAPAgX is in combination with H₂O₂The quantity ratio is 1: 2.

6. The use of the polydentate phosphine-coordinated silver complex dual emission dye according to claim 2, wherein the volume ratio of ethyl acetate to ethanol in the mixed solvent of ethyl acetate and ethanol is 1: 10.

7. Use of a polydentate phosphine coordinated silver complex bis-emissive dye according to claim 2, characterised in that in step one 1mmol polydentate phosphine, 0.7mmol AgX and 7ml DCM are mixed.

8. Use of a polydentate phosphine coordinated silver complex bis-emissive dye according to claim 2, characterised in that in step one 1mmol polydentate phosphine, 0.8mmol AgX and 8ml DCM are mixed.

9. The use of a bidentate phosphine ligand silver complex dual emission dye as claimed in claim 2, characterized in that in step two, 6mmol H is added under ice water bath₂O₂。