CN103864845A

CN103864845A - Quaternary conjugate aromatic phosphine oxide main body material, synthetic method thereof and manufacturing method of electrophosphorescent device

Info

Publication number: CN103864845A
Application number: CN201410110891.6A
Authority: CN
Inventors: 许辉; 张珍
Original assignee: Heilongjiang University
Current assignee: Heilongjiang University
Priority date: 2014-03-24
Filing date: 2014-03-24
Publication date: 2014-06-18
Anticipated expiration: 2034-03-24
Also published as: CN103864845B

Abstract

The invention discloses a quaternary conjugate aromatic phosphine oxide main body material, a synthetic method thereof and a manufacturing method of an electrophosphorescent device, and relates to an organic electroluminescent material, and synthesis and an application of the material. The material has a structure as shown in the specification. The synthetic method comprises the following steps: I, synthesis of ester; II, synthesis of a bromo-aromatic phosphine oxide compound; and III, obtaining the quaternary conjugate aromatic phosphine oxide main body material. The device disclosed by the invention comprises a substrate, a positive electrode conductive layer, a hole injection layer, a hole transmission layer a, a hole transmission layer b, a hole transmission/electron baffle layer, a luminescent layer, an electron transmission layer, an electron injection layer and a negative electrode conductive layer. According to the electrophosphorescent device manufactured by multifunctional-modified aromatic phosphine oxide as the main body material, the light voltage of the device is reduced to 2.4V, and the device has good thermodynamic stability and phase stability. The splitting temperature is 505-558 DEG C. Meanwhile, the luminous efficiency and brightness of the organic electroluminescent material are improved. The quaternary conjugate aromatic phosphine oxide main body material disclosed by the invention is mainly applied to organic electroluminescent phosphorescent diode devices.

Description

The preparation method of the large conjugation aromatic phosphines of quaternary oxygen material of main part, synthetic method and electro phosphorescent device

Technical field

The present invention relates to a kind of electroluminescent organic material, synthetic and application.

Background technology

From 1997 deng in " Nature " upper reported first the organic electro phosphorescent device taking organic transition metal title complex as twinkler, find that electromechanical phosphorescent material can utilize singlet and Triplet exciton simultaneously, its theoretical internal quantum efficiency can reach since 100%, and organic electro phosphorescent device has obtained vigorous growth.In recent years, the organic electrophosphorescenpolymer diode (PhLEDs) based on large conjugation fragrance material of main part because the little quality of its volume is light, the outstanding advantage such as high, the fast response time of deflection, luminous efficiency, solution processable enjoys people's concern.But, being subject to the impact of triplet, the kind that can be used for large conjugation fragrance material of main part is few.In particular for the material of main part of blue emitting phosphor electroluminescent device still less.And research shows that the triplet excitation state energy level of material of main part and carrier injection/transmittability thereof are two principal elements that affect doping type electro phosphorescent device performance.Have the material of main part of higher triplet, often have wider energy gap, the latter often causes the driving voltage of electro phosphorescent device higher.Therefore, how to design that to have the large conjugation fragrance material of main part that high triplet and good carrier injection/transmittability have both be problem in science urgently to be resolved hurrily.

Summary of the invention

The material of main part the object of the invention is in order to solve existing higher triplet has wider energy gap, cause the higher technical problem of driving voltage of electro phosphorescent device, the preparation method of the large conjugation aromatic phosphines of a kind of quaternary oxygen material of main part, synthetic method and electro phosphorescent device is provided.

The mode that the large conjugation aromatic phosphines of quaternary oxygen material of main part interrupts with indirect link, minor axis modification and Conjugate Multiple builds, and the structural formula of the large conjugation aromatic phosphines of quaternary oxygen material of main part is as follows:

in structural formula, x is 4-diphenylphosphine oxygen base diphenylene-oxide, 4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, 4-diphenylphosphine oxygen base dibenzothiophene or 4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene; In structural formula, Y is 4-diphenylphosphine oxygen base diphenylene-oxide, 4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, N-phenyl carbazole base, carbazyl, 4-diphenylphosphine oxygen base dibenzothiophene or 4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene.

The synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

-bis-pairs of bromophenyl fluorenes of 9,9 of 1mmol ' are dissolved in 8ml tetrahydrofuran (THF), are cooled to after-78 DEG C until solution, slowly drip 3mmol n-Butyl Lithium, control reacting liquid temperature at-78 DEG C, react 1～1.5 hour, then in system, drip 6mmol triisopropyl borate ester, continue to maintain the temperature at-78 DEG C, react 1～1.5 hour, be cooled to room temperature, and react 24～36 hours, then system is cooled to 0 DEG C, in system, drips the saturated NH of 12mmol ₄the Cl aqueous solution, at room temperature reaction 12～24h, then by reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, obtain thick product, in thick product, add 8ml benzene, 9mmol tetramethyl ethylene ketone, heating reflux reaction 6～10 hours, by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, can obtain 9,9 '-bis-pairs of phenyl fluorenes boric acid esters;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2～6ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2～4h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, can obtain bromo aromatic phosphines oxygen compound;

Three, 9 of the 1mmol being prepared by step 1,9 '-bis-pairs of phenyl fluorenes boric acid esters are dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and the tetrakis triphenylphosphine palladium of preparing in step 2, press again NaOH and 9,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substances inject than the ratio that is 6 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C～95 DEG C stirring reaction 20～30h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, then taking ethyl acetate and methyl alcohol volume ratio as (mixed solvent of 10～30) ﹕ 1 is as eluent, and column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part;

The wherein bromo aromatic phosphines oxygen compound and 9 described in step 3,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substance ratios are 3 ﹕ 1, Tetrabutyl amonium bromide and 9,9-bis-is 0.1 ﹕ 1 to phenyl fluorenes boric acid ester amount of substance ratio, tetrakis triphenylphosphine palladium and 9,9-bis-are 0.1 ﹕ 1 to phenyl fluorenes boric acid ester amount of substance ratio;

Fragrant diphenylphosphine oxygen compound described in step 2 is 4-diphenylphosphine oxygen base diphenylene-oxide, 4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, 4-diphenylphosphine oxygen base dibenzothiophene or 4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene;

Bromo aromatic phosphines oxygen compound described in step 2 is bromo diphenylphosphine oxygen base diphenylene-oxide or bromo diphenylphosphine oxygen base dibenzothiophene.

Described bromo diphenylphosphine oxygen base diphenylene-oxide is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is or 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, its structural formula is

Described bromo diphenylphosphine oxygen base dibenzothiophene is the bromo-4-diphenylphosphine of 8-oxygen base dibenzothiophene, and its structural formula is or 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene, its structural formula is

One, synthesizing of 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1～1.5 hour, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1～1.5 hour, be cooled to room temperature, and react 24～36 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12～24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6～8h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2～6ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2～4h, then uses CH successively ₂cl ₂and H ₂o extraction, obtains organic layer, organic layer is used and puts into Rotary Evaporators after anhydrous sodium sulfate drying and be spin-dried for, then purify with column chromatography using ethyl acetate as eluent, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5～20ml, add bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium, inject than the ratio that is 3 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance in NaOH, be heated to 85 DEG C～95 DEG C, stirring reaction 20～30h, then uses CH successively ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, then taking ethyl acetate and methyl alcohol volume ratio as (mixed solvent of 20～30) ﹕ 1 is as eluent, and column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Wherein the bromo aromatic phosphines oxygen compound described in step 3 is 1.5 ﹕ 1 with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance ratio, Tetrabutyl amonium bromide is 0.1 ﹕ 1 with bromo aromatic phosphines oxygen compound amount of substance ratio, and tetrakis triphenylphosphine palladium is 0.1 ﹕ 1 with bromo aromatic phosphines oxygen compound amount of substance ratio;

Described bromo diphenylphosphine oxygen base diphenylene-oxide is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is

or 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, its structural formula is

Described bromo diphenylphosphine oxygen base dibenzothiophene is the bromo-4-diphenylphosphine of 8-oxygen base dibenzothiophene, and its structural formula is

or 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene, its structural formula is

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1～1.5 hour, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1～1.5 hour, reaction system returns to room temperature, and reacts 24～36 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12～24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6～8h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2～6ml mass concentration, obtain above-mentioned sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2～4h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium again by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C～95 DEG C stirring reaction 20～30h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, then taking ethyl acetate and methyl alcohol volume ratio as (mixed solvent of 20～30) ﹕ 1 is as eluent, and column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Wherein the bromo aromatic phosphines oxygen compound described in step 2 is 1.5 ﹕ 1 with 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance ratio, Tetrabutyl amonium bromide is 0.1 ﹕ 1 with bromo aromatic phosphines oxygen compound amount of substance ratio, and tetrakis triphenylphosphine palladium is 0.1 ﹕ 1 with bromo aromatic phosphines oxygen compound amount of substance ratio;

Described in application rights requirement 1, the large conjugation aromatic phosphines of quaternary oxygen material of main part is prepared the method for electro phosphorescent device, it is characterized in that the preparation method of electro phosphorescent device carries out according to following steps:

One, glass or plastic through washed with de-ionized water being put into vacuum evaporation instrument, is 1 × 10 in vacuum tightness ^-6mbar, evaporation speed are 0.1～0.3nm s ^-1, the tin indium oxide that evaporation thickness is 1～100nm in glass or plastic, obtains anode conductive layer;

Two, the MoOx hole injection layer that evaporation thickness is 2～10nm on anode conductive layer;

Three, evaporation m-MTDATA(4 on hole injection layer, 4', 4''-tri-(N-3-aminomethyl phenyl-N-phenyl amino) triphenylamine) with MoOx(molybdenum oxide) mixture, obtaining thickness is the hole transmission layer a of 20～40nm, wherein the mass concentration of the MoOx in the mixture of m-MTDATA and MoOx is 15%, evaporation m-MTDATA on hole transmission layer a again, obtaining thickness is the hole transmission layer b of 5～15nm;

Four, evaporation Ir (ppz) on hole transmission layer b ₃(three-(2-phenylpyridine) closes iridium), obtains hole transport/electronic barrier layer that thickness is 5～50nm;

Five, on hole transport/electronic barrier layer, continue the luminescent layer that evaporation thickness is 5～40nm, doped iridium title complex and the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Complex of iridium described in step 5 is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic) (blue light doped iridium title complex), three-(2-phenylpyridine) closes iridium (Ir (ppy) ₃) (green glow doped iridium title complex), two (4-phenyl thieno-[3,2-C] pyridine-N, C2') (methyl ethyl diketone) close iridium (PO-01) (gold-tinted doped iridium title complex) or two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium (Ir (MDQ) ₂(acac) (ruddiness doped iridium title complex);

In described luminescent layer, complex of iridium is (6～10) ﹕ (94～90) with the massfraction ratio of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Six, evaporation Bphen(4 on luminescent layer, 7-phenylbenzene-1,10-phenanthrolene), obtain the electron transfer layer that thickness is 10～80nm;

Seven, evaporation Cs on electron transfer layer ₂cO ₃, obtain the electron injecting layer that thickness is 1～10nm;

Eight, the metal level that evaporation thickness is 1～100nm on electron injecting layer, obtains cathode conductive layer, and encapsulation, obtains electro phosphorescent device.

Metal level described in step 8 is calcium, magnesium, silver, aluminium, calcium alloy, magnesium alloy, silver alloys or aluminium alloy.

The present invention uses using fluorenes as chromophore, dibenzofuran group phosphorus oxygen or dibenzothiophene base phosphorus oxygen, phenyl carbazole, carbazole carry out the modification of multifunction to luminescent layer parent, these groups have certain hole/electron transport ability, their introducing can strengthen carrier injection and the transmittability of whole molecule, finally, by regulating the number of modification group and modify position the carrier transport ability that regulates and controls whole molecule.Thereby try to achieve balance between high triplet excitation state energy level and good carrier injection transmittability.

The aromatic phosphines oxygen material of main part that multifunction of the present invention is modified comprises following advantage for electroluminescent device:

1, keep higher triplet, ensure the effective transmission of energy from main body to object.

2, improve carrier injection and the transmittability of electroluminescent device material, the electro phosphorescent device that the fragrance list phosphine oxygen of modifying taking multifunction is prepared as material of main part by bright opening of electro phosphorescent device loss of voltage to 2.4V, there is good thermodynamic stability and phase stability, cracking temperature is 505 DEG C～558 DEG C, the luminous efficiency and the brightness that have improved electroluminescent organic material, the present invention is mainly used in organic electrophosphorescenpolymer diode component simultaneously.

Brief description of the drawings

Fig. 1 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment four, ■ represents the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Fig. 2 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment four;

Fig. 3 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment five, ■ represents the ultraviolet spectrogram in the large conjugation aromatic phosphines of quaternary oxygen material of main part dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Fig. 4 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment five;

Fig. 5 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment six, ■ represents the ultraviolet spectrogram in the large conjugation aromatic phosphines of quaternary oxygen material of main part dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Fig. 6 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment six;

Fig. 7 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment seven, ■ represents the ultraviolet spectrogram in the large conjugation aromatic phosphines of quaternary oxygen material of main part dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Fig. 8 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment seven;

Fig. 9 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment eight, ■ represents the ultraviolet spectrogram in the large conjugation aromatic phosphines of quaternary oxygen material of main part dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Figure 10 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment eight;

Figure 11 is the Ultraluminescence spectrum spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment nine, ■ represents the ultraviolet spectrogram in the large conjugation aromatic phosphines of quaternary oxygen material of main part dichloromethane solvent, ● represent the ultraviolet spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, represents that the large conjugation aromatic phosphines of quaternary oxygen material of main part is dissolved in the fluorescence spectrum figure in dichloromethane solvent, zero represents the fluorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part film, and △ represents the phosphorescence spectrum figure of the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Figure 12 is the thermogravimetric analysis spectrogram of the large conjugation aromatic phosphines of quaternary oxygen material of main part in experiment nine;

Figure 13 is the voltage-to-current density relationship song that the electricity of experiment 14 preparations causes dark blue smooth phosphorescence device;

Figure 14 is voltage-brightness relationship curve that the electricity of experiment 14 causes dark blue smooth phosphorescence device;

Figure 15 is brightness-current efficiency relation curve that the electricity of experiment 14 preparations causes dark blue smooth phosphorescence device;

Figure 16 is brightness-power efficiency relation curve that the electricity of experiment 14 preparations causes dark blue smooth phosphorescence device;

Figure 17 is current density-external quantum efficiency relation curve that the electricity of experiment 14 preparations causes dark blue smooth phosphorescence device;

Figure 18 is the electroluminescent spectrum figure that the electricity of experiment 14 preparations causes dark blue smooth phosphorescence device;

Figure 19 is the voltage-to-current density relationship song of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 20 is voltage-brightness relationship curve of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 21 is brightness-current efficiency relation curve of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 22 is brightness-power efficiency relation curve of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 23 is current density-external quantum efficiency relation curve of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 24 is the electroluminescent spectrum figure of the blue light electroluminescence phosphorescence device of experiment 15 preparations;

Figure 25 is the voltage-to-current density relationship curve of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 26 is voltage-brightness relationship curve of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 27 is brightness-power efficiency relation curve of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 28 is brightness-power efficiency relation curve of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 29 is current density-external quantum efficiency relation curve of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 30 is the electroluminescent spectrum figure of the electro-green light phosphorescence device of experiment 16 preparations;

Figure 31 is the voltage-to-current density relationship curve of the red electroluminescent phosphorescence device of experiment 17 preparations;

Figure 32 is voltage-brightness relationship curve of the red electroluminescent phosphorescence device of experiment 17 preparations;

Figure 33 is brightness-current efficiency relation curve of the red electroluminescent phosphorescence device of experiment 17 preparations;

Figure 34 is brightness-power efficiency relation curve of the red electroluminescent phosphorescence device of experiment 17 preparations;

Figure 35 is current density-external quantum efficiency relation curve of the red electroluminescent phosphorescence device of experiment 17 preparations;

Figure 36 is the electroluminescent spectrum figure of the red electroluminescent phosphorescence device of experiment 17 preparations.

Embodiment

Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.

Embodiment one: in present embodiment, the structural formula of the large conjugation aromatic phosphines of quaternary oxygen material of main part is as follows:

Embodiment two: the synthetic method of the large conjugation aromatic phosphines of the quaternary oxygen material of main part described in embodiment one is carried out according to following steps:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

-bis-pairs of bromophenyl fluorenes of 9,9 of 1mmol ' are dissolved in 8ml tetrahydrofuran (THF), are cooled to after-78 DEG C until solution, slowly drip 3mmol n-Butyl Lithium, control reacting liquid temperature at-78 DEG C, react 1～1.5 hour, then in system, drip 6mmol triisopropyl borate ester, continue to maintain the temperature at-78 DEG C, react 1～1.5 hour, be cooled to room temperature, and react 24～36 hours, then system is cooled to 0 DEG C, in system, drips the saturated NH of 12mmol ₄the Cl aqueous solution, at room temperature reaction 12～24h, then by reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, obtain thick product, in thick product, add 8ml benzene, 9mmol tetramethyl ethylene ketone, heating reflux reaction 6～10 hours, by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, can obtain 9,9 '-bis-pairs of phenyl fluorenes boric acid esters (white needles solid);

Two, bromo aromatic phosphines oxygen compound is synthetic:

Embodiment three: what present embodiment was different from embodiment two is that described bromo diphenylphosphine oxygen base diphenylene-oxide is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is

or 2-bromo-4,6 _-two (diphenylphosphine oxygen base) diphenylene-oxide, its structural formula is

or 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene, its structural formula is other is identical with embodiment two.

Embodiment four: described in embodiment one, the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1～1.5 hour, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1～1.5 hour, be cooled to room temperature, and react 24～36 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12～24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6～8h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester (white powder);

Two, bromo aromatic phosphines oxygen compound is synthetic:

Embodiment five: what present embodiment was different from embodiment four is that described bromo diphenylphosphine oxygen base diphenylene-oxide is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is

other is identical with embodiment four.

Embodiment six: described in embodiment one, the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1～1.5 hour, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1～1.5 hour, reaction system returns to room temperature, and reacts 24～36 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12～24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6～8h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester (white powder);

Two, bromo aromatic phosphines oxygen compound is synthetic:

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5～20ml, adds after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the N that volumetric molar concentration is 2mmol/mL again _aoH solution, is heated to 85 DEG C～95 DEG C stirring reaction 20～30h, then uses successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, then taking ethyl acetate and methyl alcohol volume ratio as (mixed solvent of 20～30) ﹕ 1 is as eluent, and column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part;

Embodiment seven: what present embodiment was different from embodiment six is that described bromo diphenylphosphine oxygen base diphenylene-oxide is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is

other is identical with embodiment six.

Embodiment eight: one of application embodiment one to the seven large conjugation aromatic phosphines of described quaternary oxygen material of main part is prepared the method for electro phosphorescent device and carried out according to following steps:

Three, the mixture of evaporation m-MTDATA and MoOx on hole injection layer, obtaining thickness is the hole transmission layer a of 20～40nm, wherein the mass concentration of the MoOx in the mixture of m-MTDATA and MoOx is 15%, evaporation m-MTDATA on hole transmission layer a again, obtaining thickness is the hole transmission layer b of 5～15nm;

Four, evaporation Ir (ppz) on hole transmission layer b ₃, obtain hole transport/electronic barrier layer that thickness is 5～50nm;

Six, evaporation Bphen on luminescent layer, obtains the electron transfer layer that thickness is 10～80nm;

Embodiment nine: what present embodiment was different from embodiment eight is that complex of iridium described in step 5 is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, three-(2-phenylpyridine) and closes iridium, two (4-phenyl thieno-[3,2-C] pyridine-N, C2') (methyl ethyl diketone) close iridium or two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium.Other is identical with embodiment eight.

Embodiment ten: what present embodiment was different from embodiment eight or nine is that the metal level described in rapid eight is calcium, magnesium, silver, aluminium, calcium alloy, magnesium alloy, silver alloys or aluminium alloy.Other is identical with embodiment eight or nine.

Adopt following experimental verification effect of the present invention:

Experiment one:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

-bis-pairs of bromophenyl fluorenes of 9,9 of 1mmol ' are dissolved in 8ml tetrahydrofuran (THF), are cooled to after-78 DEG C until solution, slowly drip 3mmol n-Butyl Lithium, control reacting liquid temperature at-78 DEG C, react 1 hour, then in system, drip 6mmol triisopropyl borate ester, continue to maintain the temperature at-78 DEG C, react 1 hour, be cooled to room temperature, and react 24 hours, then system is cooled to 0 DEG C, in system, drips the saturated NH of 12mmol ₄the Cl aqueous solution, at room temperature reaction 12h, then by reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, obtain thick product, in thick product, add 8ml benzene, 9mmol tetramethyl ethylene ketone, heating reflux reaction 6 hours, by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, can obtain 9,9 '-bis-pairs of phenyl fluorenes boric acid esters;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, can obtain bromo aromatic phosphines oxygen compound;

Three, 9 of the 1mmol being prepared by step 1,9 '-bis-pairs of phenyl fluorenes boric acid esters are dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and the tetrakis triphenylphosphine palladium of preparing in step 2, press again NaOH and 9,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substances inject than the ratio that is 6 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C of stirring reaction 20h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DDBFSPOF), and structural formula is:

Fragrant diphenylphosphine oxygen compound described in step 2 is 4-diphenylphosphine oxygen base diphenylene-oxide;

Bromo aromatic phosphines oxygen compound described in step 2 is the bromo-4-diphenylphosphine of 8-oxygen base diphenylene-oxide, and its structural formula is

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DDBTSPOF of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.32(t,J=6.8Hz,4H),7.83-7.80(dd,J ₁=4.8Hz,J ₂=8Hz,4H),7.77-7.72(dd,J ₁=7.2Hz,J ₂=12Hz,8H),7.65-7.63(dd，J ₁=1.2Hz,J ₂=8.4Hz,2H),7.59-7.42(m,23H),7.39(t,J=8Hz,5H),7.33ppm(t,J=7.6Hz,2H).

The Ultraluminescence spectrum spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DDBTSPOF as shown in Figure 3.

As shown in Figure 4, the cracking temperature of the large conjugation aromatic phosphines of quaternary oxygen material of main part DDBTSPOF is 528 DEG C to the thermogravimetric analysis spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DDBTSPOF as seen from the figure.

Experiment two:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

Two, bromo aromatic phosphines oxygen compound is synthetic:

Three, 9 of the 1mmol being prepared by step 1,9 '-bis-pairs of phenyl fluorenes boric acid esters are dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and the tetrakis triphenylphosphine palladium of preparing in step 2, press again NaOH and 9,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substances inject than the ratio that is 6 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C of stirring reaction 20h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DDBFDPOF), and structural formula is

Fragrant diphenylphosphine oxygen compound described in step 2 is 4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide; Bromo aromatic phosphines oxygen compound described in step 2 is that 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, and its structural formula is

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DDBFDPOF of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.303(s，2H),8.18(d，J=7.6Hz,2H),8.03-7.99(dd，J ₁=1.2Hz,J ₂=13.6Hz,2H),7.80(d,J=7.2Hz,2H),7.75-7.70(dd,J ₁=7.2Hz,J ₂=13.2Hz,2H),7.67-7.59(m，16H),7.48-7.41(m,17H),7.39-7.29ppm(m，23H).

Experiment three:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

Two, bromo aromatic phosphines oxygen compound is synthetic:

Three, 9 of the 1mmol being prepared by step 1,9 '-bis-pairs of phenyl fluorenes boric acid esters are dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and the tetrakis triphenylphosphine palladium of preparing in step 2, press again NaOH and 9,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substances inject than the ratio that is 6 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C of stirring reaction 20h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DDBTSPOF), and structural formula is:

Fragrant diphenylphosphine oxygen compound described in step 2 is 4-diphenylphosphine oxygen base dibenzothiophene;

Bromo aromatic phosphines oxygen compound described in step 2 is the bromo-4-diphenylphosphine of 8-oxygen base dibenzothiophene, and its structural formula is

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.32(t,J=6.8Hz,4H),7.83-7.80(dd,J ₁=4.8Hz,J2=8Hz,4H),7.77-7.72(dd,J1=7.2Hz,J2=12Hz,8H),7.65-7.63(dd，J ₁=1.2Hz,J ₂=8.4Hz,2H),7.59-7.42(m,23H),7.39(t,J=8Hz,5H),7.33ppm(t,J=7.6Hz,2H).

Experiment four:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

Two, bromo aromatic phosphines oxygen compound is synthetic:

Three, 9 of the 1mmol being prepared by step 1,9 '-bis-pairs of phenyl fluorenes boric acid esters are dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and the tetrakis triphenylphosphine palladium of preparing in step 2, press again NaOH and 9,9 '-bis-pairs of phenyl fluorenes boric acid ester amount of substances inject than the ratio that is 6 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C of stirring reaction 20h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DDBTDPOF), and structural formula is:

Fragrant diphenylphosphine oxygen compound described in step 2 is 4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene;

Bromo aromatic phosphines oxygen compound described in step 2 is that 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) dibenzothiophene, and its structural formula is

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DDBTDPOF of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.47(s,2H),8.35(d，J=8Hz,2H),8.02-7.98(dd,J ₁=1.2Hz,J ₂=13.6Hz,2H),7.80(d，J=7.2Hz,2H),7.77-7.72(dd,J ₁=7.2Hz,J ₂=13.2Hz,2H),7.68-7.61(m,16H),7.53-7.38(m,34H),7.30ppm(t,J=7.2Hz,6H).

Experiment five:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1 hour, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1 hour, be cooled to room temperature, and react 24 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2h, then uses CH successively ₂cl ₂and H ₂o extraction, obtains organic layer, organic layer is used and puts into Rotary Evaporators after anhydrous sodium sulfate drying and be spin-dried for, then purify with column chromatography using ethyl acetate as eluent, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5ml, add bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium, inject than the ratio that is 3 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance in NaOH, be heated to 85 DEG C, stirring reaction 20, then uses CH successively ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBFSPOFPhCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBFSPOFPhCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.30(s,1H),8.18-8.13(dd,J ₁=7.6Hz,J ₂=13.2Hz,3H),8.07-8.03(dd,J ₁=1.6Hz,J ₂=13.2Hz,1H),7.82(d,J=7.6Hz,2H),7.75(t，J=9.2Hz,3H),7.68-7.59(m,10H),7.56(d,J=8.4Hz,2H),7.51-7.39(m,15H),7.37-7.26(m，16H).

Experiment six:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1.5 hours, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1.5 hours, be cooled to room temperature, and react 36 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 8h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 6ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 4h, then uses CH successively ₂cl ₂and H ₂o extraction, obtains organic layer, organic layer is used and puts into Rotary Evaporators after anhydrous sodium sulfate drying and be spin-dried for, then purify with column chromatography using ethyl acetate as eluent, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 20ml, add bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium, inject than the ratio that is 3 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance in NaOH, be heated to 95 DEG C, stirring reaction 20～30h, then uses CH successively ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, again taking ethyl acetate and methyl alcohol volume ratio as (mixed solvent of 20～30) ﹕ 1 is as eluent, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBFDPOFPhCz), and structural formula is:

Fragrant diphenylphosphine oxygen compound described in step 2 is 4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide;

Bromo aromatic phosphines oxygen compound described in step 2 is that 2-is bromo-4,6-bis-(diphenylphosphine oxygen base) diphenylene-oxide, and its structural formula is

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBFDPOFPhCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.30(s,1H),8.18-8.13(dd,J ₁=7.6Hz,J ₂=13.2Hz,3H),8.07-8.03(dd,J ₁=1.6Hz,J ₂=13.2Hz,1H),7.82(d,J=7.6Hz,2H),7.75(t，J=9.2Hz,3H),7.68-7.59(m,10H),7.56(d,J=8.4Hz,2H),7.51-7.39(m,15H),7.37-7.26ppm(m，16H).

The Ultraluminescence spectrum spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFPhCz as shown in Figure 5.

As shown in Figure 6, the cracking temperature of the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFPhCz is 558 DEG C to the thermogravimetric analysis spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFPhCz as seen from the figure.

Experiment seven:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1.2 hours, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1.2 hours, be cooled to room temperature, and react 28 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 18 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 7h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 3ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 3h, then uses CH successively ₂cl ₂and H ₂o extraction, obtains organic layer, organic layer is used and puts into Rotary Evaporators after anhydrous sodium sulfate drying and be spin-dried for, then purify with column chromatography using ethyl acetate as eluent, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 10ml, add bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium, inject than the ratio that is 3 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance in NaOH, be heated to 90 DEG C, stirring reaction 25h, then uses CH successively ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 22 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBTSPOFPhCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTSPOFPhCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.35-8.32(q,J ₁=4.4Hz,J ₂=7.2Hz,2H),8.16(d，J=7.6Hz,2H),7.83(t,J=8Hz,3H),7.76(t,J=9.6Hz,6H),7.66-7.54(m,11H),7.50-7.26ppm(m,20H).

Experiment eight:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-phenyl carbazole phenyl fluorenes, being cooled to after-78 DEG C until solution, dripping 1.5mmol n-Butyl Lithium, is-78 DEG C at reacting liquid temperature, react 1.4 hours, then drip 3mmol triisopropyl borate ester, continue at-78 DEG C, react 1.4 hours, be cooled to room temperature, and react 30 hours, then system is cooled to 0 DEG C, in system, drip the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 22 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 8h, water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 5ml mass concentration, obtain sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 4h, then uses CH successively ₂cl ₂and H ₂o extraction, obtains organic layer, organic layer is used and puts into Rotary Evaporators after anhydrous sodium sulfate drying and be spin-dried for, then purify with column chromatography using ethyl acetate as eluent, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 15ml, add bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium, inject than the ratio that is 3 ﹕ 1 the NaOH solution that volumetric molar concentration is 2mmol/mL with 9-phenyl-9 '-phenyl carbazole phenyl fluorenes boric acid ester amount of substance in NaOH, be heated to 92 DEG C, stirring reaction 28h, then uses CH successively ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 28 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBTDPOFPhCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOFPhCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.46(s,1H),8.32(d，J=8Hz,1H),8.11(d，J=7.6Hz,2H),8.04-8.01(dd,J ₁=1.2Hz,J ₂=13.2Hz,1H),7.80-7.61(m,13H),7.56-7.47(m,13H),7.43-7.23ppm(m,22H).

The Ultraluminescence spectrum spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFPhCz as shown in Figure 7.

As shown in Figure 8, the cracking temperature of the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFPhCz is 522 DEG C to the thermogravimetric analysis spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFPhCz as seen from the figure.

Experiment nine:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1 hour, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1 hour, reaction system returns to room temperature, and reacts 24 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 12 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 6h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 2ml mass concentration, obtain above-mentioned sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 2h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium again by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 85 DEG C of stirring reaction 20h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 20 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBFSPOFCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBFSPOFCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.16(d,J=7.6Hz,2H),8.12(d,J=8Hz,2H),8.10(d,J=1.2Hz,1H),7.88-7.78(m,7H),7.62-7.59(dd,J ₁=1.8Hz,J ₂=8.6Hz,1H),7.55(t,J=8.4Hz,6H),7.47-7.35(m,19H),7.26ppm(t,J=8Hz,2H).

Experiment ten:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1.5 hours, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1.5 hours, reaction system returns to room temperature, and reacts 36 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 8h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 6ml mass concentration, obtain above-mentioned sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 4h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 5～20ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium again by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 95 DEG C of stirring reaction 30h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 30 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBFDPOFCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBFDPOFCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.31(s,1H),8.17(d,J=8Hz,1H),8.11(d,J=7.6Hz,2H),8.08-8.04(dd,J1=1.2Hz,J2=9.6Hz,1H),7.83(d,J=7.2Hz,2H),7.77-7.72(dd,J1=7.4Hz,J2=13Hz,1H),7.68-7.59(m,8H),7.52(t,J=8.4Hz,4H),7.45-7.40(m,14H),7.38-7.32(m,13H),7.26ppm(t,J=7.2Hz,2H).

The Ultraluminescence spectrum spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFCz as shown in Figure 9.

As shown in figure 10, the cracking temperature of the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFCz is 535 DEG C to the thermogravimetric analysis spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBFDPOFCz as seen from the figure.

Test 11:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1.2 hours, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1.2 hours, reaction system returns to room temperature, and reacts 28 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 18 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 7h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

It is in 98% the vitriol oil that the fragrant diphenylphosphine oxygen compound of 1mmol is dissolved in to 3ml mass concentration, obtain above-mentioned sulphuric acid soln, N-bromo-succinimide is joined in sulphuric acid soln than the ratio that is 1 ﹕ 1.2 in fragrant diphenylphosphine oxygen compound and N-bromo-succinimide amount of substance, stirring reaction 3h, then uses CH successively ₂cl ₂and H ₂o extraction obtains organic layer, puts into Rotary Evaporators and is spin-dried for, then purify with column chromatography using ethyl acetate as eluent after the organic layer obtaining use anhydrous sodium sulfate drying, obtains bromo aromatic phosphines oxygen compound;

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 10ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium again by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 90 DEG C of stirring reaction 22h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 22 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBTSPOFCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTSPOFCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.31-8.29(m,2H),8.10(d,J=7.6Hz,2H),7.82(d,J=7.2Hz,2H),7.79-7.71(m,5H),7.62-7.59(dd,J ₁=1.6Hz,J ₂=8Hz,1H),7.57-7.52(m,6H),7.49-7.32(m,21H),7.26-7.21ppm(m,6H).

Test 12:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

The 9-of 1mmol is dissolved in 8ml tetrahydrofuran (THF) bromophenyl-9 '-carbazole phenyl fluorenes, treats that solution is cooled to-78 DEG C, drip 1.5mmol n-Butyl Lithium, reacting liquid temperature maintains at-78 DEG C, react 1.4 hours, then in system, drip 3mmol triisopropyl borate ester, continue to maintain at-78 DEG C, react 1.4 hours, reaction system returns to room temperature, and reacts 30 hours, then, system is cooled to 0 DEG C, in system, drips the saturated NH of 6mmol ₄the Cl aqueous solution, room temperature reaction 24 hours, reaction solution extracted with diethyl ether, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, in thick product, add 8ml benzene, 3mmol tetramethyl ethylene ketone, heating reflux reaction 8h, then by reaction solution water, dichloromethane extraction, organic layer anhydrous Na ₂sO ₄dry, be spin-dried for, crude product acetone recrystallization, obtains 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester;

Two, bromo aromatic phosphines oxygen compound is synthetic:

Three, 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester of the 1mmol being prepared by step 1 is dissolved in the tetrahydrofuran (THF) of 18ml, add after bromo aromatic phosphines oxygen compound, Tetrabutyl amonium bromide and tetrakis triphenylphosphine palladium again by NaOH and 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester amount of substance than being that 3 ﹕ 1 inject the NaOH solution that volumetric molar concentration is 2mmol/mL, be heated to 92 DEG C of stirring reaction 28h, then use successively CH ₂cl ₂with saturated NH ₄cl aqueous solution extraction obtains organic phase, and organic phase anhydrous sodium sulfate drying, is spin-dried for, mixed solvent taking ethyl acetate and methyl alcohol volume ratio as 28 ﹕ 1 is as eluent again, column chromatography purification, obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part (DBTDPOFCz), and structural formula is:

Adopt nuclear magnetic resonance analyser to detect the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOFCz of this experiment preparation, detected result is as follows:

¹H?NMR(TMS,CDCl ₃,400MHz):δ=8.48(s,1H),8.34(d,J=8Hz,1H),8.09(d,J=7.6Hz,2H),8.04-8.00(dd,J ₁=1.6Hz,J ₂=13.6Hz,1H),7.81(d,J=7.2Hz,2H),7.73(d,J=6.8Hz,1H),7.70-7.62(m,8H),7.54-7.47(m,10H),7.45-7.31(m,21H),7.25-7.22ppm(m,2H).

The Ultraluminescence spectrum spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFCz as shown in figure 11.

As shown in figure 12, the cracking temperature of the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFCz is 529 DEG C to the thermogravimetric analysis spectrogram that this experiment obtains the large conjugation aromatic phosphines of quaternary oxygen material of main part DBTDPOFCz as seen from the figure.

Test 13:

The method that described in application experiment 12, the large conjugation aromatic phosphines of quaternary oxygen material of main part is prepared electro phosphorescent device is carried out according to following steps:

Complex of iridium described in step 5 is two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium (FIrpic), and in described luminescent layer, complex of iridium is 10 ﹕ 90 with the massfraction ratio of the large conjugation aromatic phosphines of quaternary oxygen material of main part, obtains blue light electro phosphorescent device.

Complex of iridium described in step 5 is that three-(2-phenylpyridine) closes iridium (Ir (ppy) ₃), in described luminescent layer, complex of iridium is 6 ﹕ 94 with the massfraction ratio of the large conjugation aromatic phosphines of quaternary oxygen material of main part, obtains green glow electro phosphorescent device.

Complex of iridium described in step 5 is two (4-phenyl thieno-s [3,2-C] pyridine-N, C2') (methyl ethyl diketone) closes iridium (PO-01), in described luminescent layer, complex of iridium is 6 ﹕ 94 with the massfraction ratio of the large conjugation aromatic phosphines of quaternary oxygen material of main part, obtains gold-tinted electro phosphorescent device.

Complex of iridium described in step 5 is two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium (Ir (MDQ) ₂(acac), in described luminescent layer, complex of iridium is 8 ﹕ 92 with the massfraction ratio of the large conjugation aromatic phosphines of quaternary oxygen material of main part, obtains ruddiness electro phosphorescent device.

Test 14:

The structure of blue light electroluminescence phosphorescence device prepared by the method for application experiment 13, the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 is: ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) 3] (10nm)/DBTDPOCz:FIr6 (10%, 10nm)/Bphen (40nm)/Cs2CO3 (1nm)/Al.

The complex of iridium adopting is FIr6, and its structural formula is

The voltage-to-current density relationship curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 as shown in figure 13, the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOCz that schemes thus known experiment 12 has characteristic of semiconductor, and its threshold voltage is 2.6V.

As shown in figure 14, scheme thus the bright voltage of opening of known this device is 2.6V to voltage-brightness relationship curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12, at 1083cdm ^-2～3452cdm ^-2brightness under, driving voltage is still lower than 5.8V.

As shown in figure 15, scheme thus known this device is 139.7cdm in brightness to brightness-current efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 ^-2time, current efficiency reaches maximum value 12.4cdA ^-1.

As shown in figure 16, scheme thus known this device is 50.59cdm in brightness to brightness-power efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 ^-2time, power efficiency reaches maximum value 13.5lmW ^-1.

As shown in figure 17, scheme thus known this device is 139.7mAcm in brightness to current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 ^-2time, obtain maximum external quantum efficiency 7.1%.

The electroluminescent spectrum figure of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of employing experiment 12 as shown in figure 18, schemes the electroluminescent peak of known this device thus at 460nm place, follows the acromion of 488nm.

Test 15:

What this experiment was different from experiment 14 is that the complex of iridium adulterating in step 5 luminescent layer is that two (4,6-difluorophenyl pyridine-N, C2) pyridine formyls close iridium (FIrpic), and the mass concentration of doping is 10%.Other are identical with experiment 14.

The structure of this experiment electro phosphorescent device is: ITO/MoOx (2nm)/m-MTDATA:MoOx (15%, 30nm)/m-MTDATA (10nm)/[Ir (ppz) ₃] (10nm)/DBTDPOCz:FIrpic (10%, 10nm)/Bphen (40nm)/Cs ₂cO ₃(1nm)/Al.

The voltage-to-current density relationship curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 19, the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOCz that schemes thus known experiment 12 has characteristic of semiconductor, and its threshold voltage is 2.4V.

As shown in figure 20, scheming thus the bright voltage of opening of known this device is 2.4V to blue light electroluminescence phosphorescence device voltage-brightness relationship curve prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12, at 1256cdm ^-2～7682cdm ^-2brightness under, driving voltage is still lower than 5.2V.

As shown in figure 21, scheme thus known this devices is 57.56cdm in brightness to brightness-current efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, current efficiency reaches maximum value 20.8cdA ^-1.

As shown in figure 22, scheme thus known this devices is 57.56cdm in brightness to brightness-power efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, power efficiency reaches maximum value 25.1lmW ^-1.

As shown in figure 23, scheme thus known this device is 57.56mAcm in brightness to current density-external quantum efficiency relation curve of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, obtain maximum external quantum efficiency 10.8%.

The electroluminescent spectrum figure of blue light electroluminescence phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 24, schemes the electroluminescent peak of known this device thus at 472nm place.

Test 16:

What this experiment was different from experiment 14 is that the complex of iridium adulterating in step 5 luminescent layer is that three-(2-phenylpyridine) closes iridium (Ir (ppy) ₃), the mass concentration of doping is 6%.Other are identical with experiment 14.

The structure of this experiment electro phosphorescent device is: ITO/MoO _x(2nm)/m-MTDATA:MoO _x(15%, 30nm)/m-MTDATA (10nm)/Ir (ppz) ₃(10nm)/DBTDPOFCz:Ir (ppy) ₃(6%, 10nm)/BPhen (40nm)/Cs ₂cO ₃(1nm)/Al.

The voltage-to-current density relationship curve of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 25, the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOCz that schemes thus known experiment 12 has characteristic of semiconductor, and its threshold voltage is 2.4V.

As shown in figure 26, scheme thus the bright voltage of opening of known this device is 2.4V to voltage-brightness relationship curve of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12, at 10660cdm ^-2～14140cdm ^-2brightness under, driving voltage is still lower than 5V.

As shown in figure 27, scheme thus known this device brightness is 379.8cdm to brightness-current efficiency relation curve of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, current efficiency reaches maximum value 36.6cdA ^-1.

As shown in figure 28, scheme thus known this device is 51.81cdm in brightness to brightness-power efficiency relation curve of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, power efficiency reaches maximum value 41.9lmW ^-1.

As shown in figure 29, scheme thus known this device is 379.8mAcm in brightness to current density-external quantum efficiency relation curve of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, obtain maximum external quantum efficiency 10.7%.

The electroluminescent spectrum figure of electro-green light phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 30, schemes the electroluminescent peak of known this device thus at 516nm place.

Test 17:

What this experiment was different from experiment 14 is that the complex of iridium adulterating in step 5 luminescent layer is two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium (Ir (MDQ) ₂(acac)), the mass concentration of doping is 8%.Other are identical with experiment 14.

The structure of this experiment electro phosphorescent device is: ITO/MoO _x(2nm)/m-MTDATA:MoO _x(15%, 30nm)/m-MTDATA (10nm)/Ir (ppz) ₃(10nm)/DBTDPOCz:Ir (MDQ) ₂(acac) (8%, 10nm)/BPhen (40nm)/Cs ₂cO ₃(1nm)/Al.

The voltage-to-current density relationship curve of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 31, the large conjugation aromatic phosphines of the quaternary oxygen material of main part DBTDPOCz material of scheming thus known experiment 12 has characteristic of semiconductor, and its threshold voltage is 2.2V.

Shown in figure 32, scheme thus the bright voltage of opening of known this device is 2.2V to voltage-brightness relationship curve of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12, at 1208cdm ^-2～3318cdm ^-2brightness under, driving voltage is still lower than 5.6V.

As shown in figure 33, scheme thus known this device is 24.92cdm in brightness to brightness-current efficiency relation curve of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, current efficiency reaches maximum value 5.8cdA ^-1.

As shown in figure 34, scheme thus known this device is being 6.486cdm in brightness to brightness-power efficiency relation curve of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, power efficiency reaches maximum value 7.5lmW ^-1.

As shown in figure 35, scheme thus known this device is 24.92mAcm in brightness to current density-external quantum efficiency relation curve of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 ^-2time, obtain maximum external quantum efficiency 5.0%.

The electroluminescent spectrum figure of red electroluminescent phosphorescence device prepared by the large conjugation aromatic phosphines of the quaternary oxygen material of main part of this experiment employing experiment 12 as shown in figure 36, schemes the electroluminescent peak of known this device thus at 616nm place.

Claims

1. the large conjugation aromatic phosphines of quaternary oxygen material of main part, is characterized in that the structural formula of the large conjugation aromatic phosphines of described quaternary oxygen material of main part is as follows:

2. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part described in claim 1, is characterized in that the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

One, 9,9 '-bis-pairs of phenyl fluorenes boric acid esters is synthetic:

Two, bromo aromatic phosphines oxygen compound is synthetic:

3. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part according to claim 2, is characterized in that:

4. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part described in claim 1, is characterized in that the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

Two, bromo aromatic phosphines oxygen compound is synthetic:

5. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part according to claim 4, is characterized in that:

6. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part described in claim 1, is characterized in that the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part is carried out according to following steps:

One, synthesizing of 9-phenyl-9 '-carbazole phenyl fluorenes boric acid ester:

Two, bromo aromatic phosphines oxygen compound is synthetic:

7. the synthetic method of the large conjugation aromatic phosphines of quaternary oxygen material of main part according to claim 6, is characterized in that:

8. application rights requires the large conjugation aromatic phosphines of quaternary oxygen material of main part described in 1 to prepare the method for electro phosphorescent device, it is characterized in that the preparation method of electro phosphorescent device carries out according to following steps:

9. the preparation method of electro phosphorescent device according to claim 8, it is characterized in that complex of iridium described in step 5 is for two (4,6-difluorophenyl pyridine-N, C2) pyridine formyl closes iridium, three-(2-phenylpyridine) and closes iridium, two (4-phenyl thieno-[3,2-C] pyridine-N, C2') (methyl ethyl diketone) close iridium or two (2-methyl-dibenzo quinoxalinyl)-methyl ethyl diketone iridium.

10. the preparation method of electro phosphorescent device according to claim 8, is characterized in that the metal level described in step 8 is calcium, magnesium, silver, aluminium, calcium alloy, magnesium alloy, silver alloys or aluminium alloy.